Method for manufacturing photochromic contact lenses

Abstract

A method for manufacturing a contact lens comprising a central photochromic zone having a diameter of about 13 mm or less that is concentric with the central axis of the contact lens is described herein. The method comprises the steps of: applying a droplet of a first polymerizable fluid composition (having a volume of about 5 μL or less) containing at least one photochromic compound and a relatively high molecular weight polysiloxane vinyl crosslinking agent to the center of the molding surface of a male mold half to increase viscosity and adhesion to the molding surface of a male mold half; administering a second polymerizable fluid composition to a female mold half; closing the female mold half with the droplet to form a molded assembly; and curing the droplet of the second polymerizable fluid composition and the first polymerizable fluid composition in the molded assembly.

Description

Technology Field

[0001] The present invention relates to a method for manufacturing a silicone hydrogel contact lens having a photochromic central region. The present invention also provides a silicone hydrogel contact lens manufactured according to the method of the present invention. Background Technology

[0002] Typically, UV-absorbing compounds are incorporated into contact lenses to manufacture UV-absorbing contact lenses that protect the eyes from ultraviolet rays. Recently, various photochromic contact lenses for protecting the eyes from ultraviolet rays have been proposed (see, for example, U.S. Patents No. 4681412, 6017121, 6174464, 6224945, 7261844, 7368072, 7556750, 7560056, 7584630, 7641337, 7999989, 8158037, 8697770, 8741188, 9052438, 9097916, 9377569, 9465234, 9904074, 10197707). These proposed photochromic contact lenses include a photochromic compound that can undergo reversible discoloration, for example, from "clear" to blue or other colors, upon exposure to UV / HEVL radiation.

[0003] Generally, photochromic contact lenses can be obtained by adding a photochromic compound to a polymerizable composition (i.e., lens formulation) for forming a contact lens, and then curing the polymerizable composition in a contact lens mold according to a cast-molded lens manufacturing process. A typical cast-molded lens manufacturing process includes the following steps: a single curing (polymerization) step of a single polymerizable composition (lens formulation) within a single-use plastic mold, generally composed of two single-molded halves; a mold opening step; optionally but preferably a lens delensing step (i.e., removing the cast-molded lens from the mold); and various post-molding process application steps, including extraction, hydration, packaging, sterilization, etc.

[0004] However, photochromic contact lenses obtained by such conventional cast-molding processes have a photochromic compound uniformly incorporated within the polymer matrix of the photochromic contact lens and may undergo reversible discoloration upon exposure to UV / HEVL radiation from edge to edge. Such photochromic contact lenses are undesirable for cosmetic reasons. It would be desirable to produce photochromic contact lenses that change color only in the central pupil area.

[0005] U.S. Patents No. 7368072, 7560056, 8697770, and 9904074 disclose a method for manufacturing a photochromic contact lens in which only the central pupil region may undergo reversible discoloration upon exposure to UV / HEVL radiation. This method comprises the following steps: introducing a photochromic lens-forming composition into the central region of the molding surface of a mold half, and then adding a clear lens-forming composition on top of the photochromic lens-forming composition (the photochromic lens-forming composition has a much higher viscosity than the clear lens-forming composition); aligning with the other mold half to form a cavity having the photochromic clear lens-forming composition inside; and curing the photochromic clear lens-forming composition within the cavity of the mold to form a photochromic contact lens. However, handling and introducing high-viscosity photochromic lens-forming compositions may be difficult in a production environment.

[0006] Therefore, there is still a need for a method to manufacture photochromic silicone hydrogel contact lenses in which only the central pupil region undergoes reversible discoloration upon exposure to UV / HEVL radiation.

[0007] The present invention provides a method for manufacturing a silicone hydrogel contact lens, comprising, in some embodiments, the following steps: (1) obtaining a first polymerizable fluid composition and a second polymerizable fluid composition (the first polymerizable fluid composition comprises at least one free radical initiator, at least one first polymerizable material, and at least one photochromic compound, wherein the at least one polymerizable material comprises at least one first polysiloxane vinyl crosslinker having a weight average molecular weight of at least 5000 daltons and present in the first polymerizable composition in an amount of at least 40 weight%, and the second polymerizable fluid composition comprises the at least one free radical initiator and at least one second polymerizable material and is free of any photochromic compound); (2) obtaining a lens mold comprising a male mold half having a first molding surface defining the rear surface of the contact lens to be molded and a female mold half having a second molding surface defining the front surface of the contact lens to be molded, wherein the female and male mold half accommodate each other when the mold is closed to form a mold cavity between the first and second molding surfaces; (3) applying a droplet of a first polymerizable fluid composition onto the geometric center of the first molding portion of the male mold half (the volume of the droplet is about 5 μL or less); (4) dispensing a predetermined amount of a second polymerizable fluid composition onto the second molding surface of the female mold half; (5) closing the female mold half with the male mold half to which the droplet is attached to form a molded assembly comprising the second polymerizable composition and the droplet of the first polymerizable composition within the mold cavity; (6) A step of curing droplets of the second polymerizable fluid composition and the first polymerizable composition to form a raw silicone hydrogel contact lens having a photochromic central region, wherein the photochromic central region has a diameter of about 13 mm or less and is concentric with the central axis of the raw silicone hydrogel contact lens;(7) a step of separating the molded assembly into a male mold half and a female mold half with a raw silicone hydrogel contact lens attached to a lens-attached mold half, which is one of the male and female mold halfs; (8) a step of removing the raw silicone hydrogel contact lens from the lens-attached mold half; and (9) a step of applying the raw silicone hydrogel contact lens to a post-molding process comprising a hydration process and one or more other processes selected from the group consisting of extraction, surface treatment, packaging, sterilization, and combinations thereof.;

[0008] In another embodiment, the present invention provides a silicone hydrogel contact lens manufactured according to the method of the present invention. Brief explanation of the drawing

[0009] FIG. 1 schematically illustrates a hydrogel contact lens according to a preferred embodiment of the present invention. Specific details for implementing the invention

[0010] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. In general, the nomenclature and laboratory procedures used herein are widely known and commonly used in the art. Conventional methods, such as those provided in the art and various general references, are used for these procedures. Where a term is provided in the singular form, the inventors also consider the plural form of the term. The nomenclature used herein and the laboratory procedures described below are widely known and commonly used in the art.

[0011] As used herein, “about” means that the number referred to as “about” includes 1 to 10% of the cited number added to or subtracted from the cited number.

[0012] "Optional" or "arbitrarily" means that the event or situation described later may or may not occur, and implies that the description includes cases where the event or situation occurs and cases where the event or situation does not occur.

[0013] "Contact lens" refers to a structure that may be placed on or within the wearer's eye. A contact lens may correct, improve, or alter the user's vision, but is not necessarily so. A contact lens may be any suitable material known in the art or subsequently developed, and may be a soft lens, a hard lens, or a hybrid lens.

[0014] "Hydrogel contact lens" refers to a contact lens comprising a hydrogel bulk (core) material. The hydrogel bulk material may be a non-silicone hydrogel material or, preferably, a silicone hydrogel (SiHy) material.

[0015] "Hydrogel" or "hydrogel material" refers to a cross-linked polymer material having a three-dimensional polymer network (i.e., a polymer matrix) that is insoluble in water but can retain 10 weight percent or more of water within its polymer matrix when fully hydrated (or equilibrated).

[0016] "Silicone hydrogel" or "SiHy" refers to a silicon-containing hydrogel obtained by copolymerizing a polymerizable composition comprising at least one silicon-containing vinyl monomer and / or at least one silicon-containing vinyl crosslinking agent.

[0017] As is known to those skilled in the art, “siloxane” or “silicon” interchangeably refers to a molecule having a -Si-O-Si- moiety in which each Si atom is accompanied by at least two substituents (organic groups) or at least one -Si-O-Si- moiety.

[0018] As used in this application, the term "non-silicon hydrogel" refers to a hydrogel that is theoretically free of silicon.

[0019] As used herein, "hydrophilic" describes a material or part thereof that associates more readily with water than lipids.

[0020] "Vinyl monomer" refers to a compound having one single ethylene-based unsaturated group, being soluble in a solvent, and capable of being polymerized by chemical rays or heat.

[0021] With respect to a compound or substance in a solvent, the term "soluble" means that the compound or material is dissolved in the solvent and can provide a solution at a concentration of about 0.5 weight% or more at room temperature (i.e., a temperature of about 22°C to about 26°C).

[0022] With respect to a compound or substance in a solvent, the term "insoluble" means that the compound or substance is dissolved in the solvent and can provide a solution at a concentration of less than 0.01 weight% at room temperature (as defined above).

[0023] The term "ethylenically unsaturated group" is used herein in a broad sense and is intended to encompass any group containing at least one >C=C< group. Exemplary ethylenically unsaturated groups include, without limitation, (meth)acryloyl ( and / or ), allyl, vinyl, styrenyl, or other C=C containing groups are included.

[0024] As used herein, in relation to the curing, crosslinking, or polymerization of a polymerizable composition, prepolymer, or material, "by chemical rays" means that curing (e.g., crosslinking and / or polymerization) is performed by chemical ray irradiation, such as, for example, UV / visible light irradiation. Thermal curing or chemical ray curing methods are well known to those skilled in the art.

[0025] "Acrylic monomer" refers to a vinyl monomer having a single (meth)acryloyl group. Examples of acrylic monomers include (meth)acryloxy [or (meth)acryloyloxy] monomers and (meth)acrylamido monomers.

[0026] "(Met)acryloxy monomer" or "(Met)acryloyloxy monomer" is or It refers to a vinyl monomer having a single group.

[0027] "(Met)acrylamido monomer" is or (Here, R o It refers to a vinyl monomer having one single group (which is H or C1-C4 alkyl).

[0028] The term "(meth)acrylamide" refers to methacrylamide and / or acrylamide.

[0029] The term "(meth)acrylate" refers to methacrylates and / or acrylates.

[0030] "N-vinyl amide monomer" is a vinyl group directly attached to the nitrogen atom of the amide group ( It refers to amide compounds having ).

[0031] "En monomer" refers to a vinyl monomer having a single en group.

[0032] "Hydrophilic vinyl monomer," "hydrophilic acrylic monomer," "hydrophilic (meth)acryloxy monomer," or "hydrophilic (meth)acrylamido monomer" each refers to a vinyl monomer, an acrylic monomer, a (meth)acryloxy monomer, or a (meth)acrylamido monomer that, as used herein, generally produces a homopolymer that is water-soluble or capable of absorbing 10 weight percent or more of water.

[0033] "Hypothecolytic vinyl monomer," "hydrophobic acrylic monomer," "hydrophobic (meth)acryloxy monomer," or "hydrophobic (meth)acrylamido monomer" respectively refer to a vinyl monomer, an acrylic monomer, a (meth)acryloxy monomer, or a (meth)acrylamido monomer that, as used herein, generally produces a homopolymer that is insoluble in water and capable of absorbing less than 10 weight percent of water.

[0034] As used in this application, the term “vinyl crosslinker” refers to an organic compound having at least two ethylene-based unsaturated groups. “Vinyl crosslinker” refers to a vinyl crosslinker having a molecular weight of 700 daltons or less.

[0035] "Polysiloxane segment" or "polydiorganosiloxane segment" are interchangeable It refers to a polymer chain segment (i.e., a divalent radical), where SN is an integer greater than or equal to 3, and R S1 and R S2 Each is independently C1-C 10 Alkyl; Phenyl; C1-C4-alkyl-substituted phenyl; C1-C4-alkoxy-substituted phenyl; Phenyl-C1-C6-alkyl; C1-C 10 Fluoroalkyl; C1-C 10 Fluoroether; aryl; aryl C1-C 18 Alkyl; -alk-(OC2H4) γ1 -OR o (Here, alk is a C1-C6 alkylene diradal, and R o is H or C1-C4 alkyl and γ1 is an integer from 1 to 10); hydroxyl group (-OH), carboxyl group (-COOH), -NR N1 -'s amino linker, -CONR N1 -amide linker of, -CONR N1 R N1 amide of, -OCONH- urethane linker, and C1-C4 alkoxy group, or linear hydrophilic polymer chain (where, R N1 and R N1' are independently hydrogen or C1-C 15 C2-C having at least one functional group selected from the group consisting of alkyls 40 It is selected from a group consisting of organic radicals.

[0036] "Polydiorganosiloxane vinyl crosslinker" or "polysiloxane vinyl crosslinker" interchangeably refers to a compound comprising at least one polysiloxane segment and at least two ethylene-based unsaturated groups.

[0037] "Linear polydiorganosiloxane vinyl crosslinker" or "linear polysiloxane vinyl crosslinker" interchangeably refers to a compound comprising a main chain that is terminated by one ethylene-based unsaturated group at each of the two ends of the main chain and comprises at least one polysiloxane segment.

[0038] "Chain-extended polydiorganosiloxane vinyl crosslinker" or "chain-extended polysiloxane vinyl crosslinker" interchangeably refers to a compound comprising at least two ethylene-based unsaturated groups and at least two polysiloxane segments (each pair of these is connected by one divalent radical).

[0039] The term "photochromic vinyl monomer" refers to a vinyl monomer having one colorless (or pale) form and one colored form, which can undergo a reversible change from the colorless form (or pale form) (or so-called "inactive form") to the colored form (or so-called "activated form") upon exposure to UV / HEVL radiation.

[0040] In relation to photochromic contact lenses, the terms "colorless or pale state" or "inactive state" refer to the original state of the photochromic contact lens prior to irradiation with UV / HEVL light. In this state, the photochromic contact lens is generally colorless or exhibits a faint color as observed with the naked eye.

[0041] In relation to photochromic contact lenses, the terms "tinted state" or "active state" refer to the state of a photochromic contact lens when irradiated with UV / HEVL light. In this state, the photochromic contact lens generally exhibits a dark color, as observed with the naked eye.

[0042] As used herein, the term "fluid" indicates that the material can flow like a liquid.

[0043] As used herein, the term “transparent” in relation to a polymerizable composition means that the polymerizable composition is a transparent solution or liquid mixture having a light transmittance of 85% or more (preferably 90% or more) in the range of 400 to 700 nm.

[0044] A free radical initiator may be either a photoinitiator or a thermal initiator. "Photoinitiator" refers to a chemical substance that initiates a free radical crosslinking / polymerization reaction using UV and / or visible light. "Thermal initiator" refers to a chemical substance that initiates a radical crosslinking / polymerization reaction using thermal energy.

[0045] The term "acyl germanium photoinitiator" refers to an organic germanium compound that is a germanium-based Norrish Type I photoinitiator and comprises one or more acrylcarbonyl groups connected to germanium. Examples of such acyl germanium photoinitiators are disclosed in U.S. Patents No. 7605190 and No. 10324311.

[0046] As used in this application, the term "polymer" means a material formed by polymerizing or crosslinking one or more monomers, macromonomers, prepolymers, or combinations thereof.

[0047] "Macromonomer" or "prepolymer" refers to a compound or polymer containing an ethylene-based unsaturated group and having a number average molecular weight of more than 700 daltons.

[0048] As used in this application, the term “molecular weight” of a polymeric material (including monomeric or macromonomeric materials) refers to the number average molecular weight unless specifically stated otherwise or otherwise indicated in the test conditions. Those skilled in the art will know of methods, e.g., gel permeation chromatography (GPC) using one or more of a refractive index detector, a low-angle laser light scattering detector, a multi-angle laser light scattering detector, a differential viscometer detector, a UV detector, and an infrared (IR) detector; and matrix-assisted desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS). 1 I know how to measure the molecular weight of polymers using methods such as ¹H NMR (proton nuclear magnetic resonance) spectroscopy.

[0049] The term "monovalent radical" refers to an organic radical obtained by removing a hydrogen atom from an organic compound and forming a bond with one other group within the organic compound. Examples include, without limitation, alkyl (by removing a hydrogen atom from an alkane), alkoxy (or alkoxyl) (by removing one hydrogen atom from the hydroxyl group of an alkyl alcohol), thiyl (by removing one hydrogen atom from the thiol group of an alkylthiol), cycloalkyl (by removing a hydrogen atom from a cycloalkane), cycloheteroalkyl (by removing a hydrogen atom from a cycloheteroalkane), aryl (by removing a hydrogen atom from the aromatic ring of an aromatic hydrocarbon), heteroaryl (by removing a hydrogen atom from any ring atom), amino (by removing one hydrogen atom from an amine), etc.

[0050] The term "divalent radical" refers to an organic radical obtained by removing two hydrogen atoms from an organic compound and forming two bonds with two other groups within the organic compound. For example, the alkylene divalent radical (i.e., alkylenyl) is obtained by removing two hydrogen atoms from an alkane, and the cycloalkylene divalent radical (i.e., cycloalkylenyl) is obtained by removing two hydrogen atoms from a cyclic ring.

[0051] In this application, the term “substituted” with respect to alkyl or alkylenyl means that the alkyl or alkylenyl replaces one hydrogen atom of the alkyl or alkylenyl and comprises at least one substituent selected from the group consisting of hydroxyl (-OH), carboxyl (-COOH), -NH2, sulfhydryl (-SH), C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio(alkyl sulfide), C1-C4 acylamino, C1-C4 alkylamino, di-C1-C4 alkylamino, and combinations thereof.

[0052] The term "terminal ethylene unsaturated group" refers to one ethylene unsaturated group at one of the two ends of the main chain (or backbone) of an organic compound as known to those skilled in the art.

[0053] "Blending vinyl monomer" refers to a vinyl monomer capable of dissolving both the hydrophilic and hydrophobic components of a polymerizable composition to form a solution.

[0054] In relation to SiHy contact lenses, "post-curing surface treatment" refers to a surface treatment process performed after the SiHy contact lens is formed by curing the SiHy lens formulation (i.e., polymerizing by heat or chemical radiation).

[0055] The terms "silicone hydrogel lens formulation" or "SiHy lens formulation" refer, interchangeably, to a polymerizable composition comprising all polymerizable components necessary to produce a SiHy contact lens or SiHy lens material, as is well known to those skilled in the art.

[0056] "UV absorbing vinyl monomer" means a compound comprising a UV absorbing moiety and an ethylene-based unsaturated group capable of absorbing or filtering UV radiation in the range of 200 nm to 400 nm, as understood by those skilled in the art.

[0057] "HEVL absorbing vinyl monomer" means a compound comprising an ethylene-based unsaturated group and an HEVL absorbing moiety capable of absorbing or filtering HEVL (high-energy-violet-light) radiation in the range of 380 nm to 440 nm, as understood by those skilled in the art.

[0058] "UVA" refers to radiation occurring at a wavelength of 315 to 380 nanometers; "UVB" refers to radiation occurring at a wavelength of 280 to 315 nanometers; and "Violet" refers to radiation occurring at a wavelength of 380 to 440 nanometers.

[0059] "UVA transmittance" (or "UVA %T"), "UVB transmittance" or "UVB %T", and "Violet transmittance" or "Violet %T" are calculated by the following formula.

[0060] UVA %T = Average transmittance between 315 nm and 380 nm % x 100

[0061] UVB %T = Average transmittance between 280 nm and 315 nm % x 100

[0062] Violet %T = Average transmittance between 380 nm and 440 nm % x 100

[0063] Intrinsic "oxygen permeability" of the material, Dk iε is the rate at which oxygen passes through a material. As used herein, in relation to hydrogels (silicone or non-silicone) or contact lenses, the term "oxygen permeability (Dk)" refers to the corrected oxygen permeability (Dk), measured at about 34°C to 35°C according to the procedure described in ISO 18369-4 and corrected for surface resistance to oxygen flux induced by boundary layer effects. c It means ). Oxygen permeability is typically expressed in bars, and "bar" is [(cm 3 Oxygen)(cm) / (cm 2 )(sec)(mm Hg)] x 10 -9 It is defined as.

[0064] The "oxygen permeability" of a lens or material, Dk / t, is the rate at which oxygen passes through a specific lens or material with an average thickness t [in mm] over the measured area. Oxygen permeability is typically expressed in units of barr / mm, and "barr / mm" is [(cm 3 Oxygen) / (cm² 2 )(sec)(mm Hg)] x 10 -9 It is defined as.

[0065] In relation to contact lenses or materials, the terms "modulus" or "elastic modulus" refer to the tensile modulus or Young's modulus, which is a measure of the stiffness of the contact lens or material under tension. Methods for measuring the elastic modulus of SiHy materials or contact lenses are widely known to those skilled in the art. For example, all commercial contact lenses have a measured elastic modulus.

[0066] "Unprocessed state" refers to a contact lens obtained by casting-molding a polymerizable composition in a mold and not undergoing post-molding processes of extraction and / or hydration (i.e., not coming into contact with water or any organic solvent or any liquid after molding).

[0067] "Hand mold half" or "base curve mold half" refers interchangeably to a mold half having a molded surface that is a substantially convex surface defining the rear surface of a contact lens.

[0068] "Female mold half" or "front curved mold half" refers interchangeably to a mold half having a molded surface that is a substantially concave surface defining the front surface of a contact lens.

[0069] As used in this application, the terms “anterior surface,” “front surface,” “front surface,” or “FC surface” in relation to contact lenses refer interchangeably to the surface of the contact lens facing away from the eye during wear. The anterior surface (front surface) is generally substantially convex.

[0070] As used in this application, the terms “rear surface,” “back surface,” “base surface,” or “BC surface” in relation to contact lenses refer interchangeably to the surface of a contact lens or insert facing the eye during wear. The rear surface (back surface) is generally substantially concave.

[0071] In relation to contact lenses, "coating" means that the contact lens has a thin layer of material on its surface that is different from the bulk material of the contact lens and is obtained by surface treating the contact lens.

[0072] As used herein, "surface modification" or "surface treatment" means that the article has been treated by a surface treatment process that (1) applies a coating to the surface of the article, (2) adsorbs chemical species onto the surface of the article, (3) changes the chemical properties of chemical groups on the surface of the article (e.g., electrostatic charge), or (4) modifies the surface characteristics of the article differently. Exemplary surface treatment processes include, but are not limited to, surface treatment by energy (e.g., plasma, electrostatic charge, radiation, or other energy source), chemical treatment, grafting of a hydrophilic vinyl monomer or macromonomer onto the surface of an article, the mold transfer coating process disclosed in U.S. Patent No. 6719929, the incorporation of a wetting agent into a lens formulation for manufacturing contact lenses proposed in U.S. Patents No. 6367929 and No. 6822016, the reinforced mold transfer coating disclosed in U.S. Patent No. 7858000, and a hydrophilic coating consisting of the covalent attachment or physical deposition of one or more layers of one or more hydrophilic polymers onto the surface of a contact lens disclosed in U.S. Patents No. 8147897, No. 8409599, No. 8557334, No. 8529057, and No. 9505184.

[0073] In relation to a material or contact lens, "hydrophilic surface" means that the material or contact lens has surface hydrophilicity characterized by having an average water contact angle of about 90 degrees or less, preferably about 80 degrees or less, more preferably about 70 degrees or less, and more preferably about 60 degrees or less.

[0074] "Average contact angle" means the water contact angle obtained by averaging the measurements of at least three individual contact lenses (static water contact angle measured by Sessile Drop).

[0075] In relation to contact lenses, the term "central axis" refers to a line passing through the geometric center of the anterior and posterior surfaces of the contact lens.

[0076] Generally, the present invention relates to a method for manufacturing contact lenses, particularly SiHy contact lenses, wherein each contact lens comprises a central photochromic zone having a diameter of about 13 mm or less that is concentric with the central axis of the contact lens.

[0077] FIG. 1 schematically illustrates a SiHy contact lens of the present invention. SiHy contact lens ( 100 ) is the front surface( 102 ), opposite rear surface, central axis( 101 ), and SiHy contact lenses ( 100 The central axis of ) 101 Diameter concentric with ) 120 central area having ) 110 Includes ). Central zone( 110 ) is the rear part( 112 It includes at least one photochromic compound distributed in the peripheral area (including the central part of the rear surface) and providing photochromic functionality to the central area.

[0078] The present invention is partially based on the discovery that such contact lenses can be manufactured according to a process comprising: applying a droplet of a first polymerizable fluid composition containing at least one photochromic compound and a relatively high molecular weight polysiloxane vinyl crosslinking agent to the center of the molding surface of a male mold half to increase viscosity and adhesion to the molding surface of a male mold half; administering a second polymerizable fluid composition to a female mold half; closing the female mold half with the droplet to form a molded assembly; and curing the droplet of the second polymerizable fluid composition and the first polymerizable fluid composition in the molded assembly.

[0079] It has been found that by selecting a polysiloxane vinyl monomer with an average molecular weight and a predetermined amount, the viscosity of the first polymerizable fluid composition and the adhesion to the molding surface of the male mold half can be sufficiently increased so that when the male and female mold halves are closed to form a molded assembly, a droplet of the first polymerizable composition is applied to the molding surface and does not diffuse into the second polymerizable fluid composition in the female mold half. This can be achieved by controlling the amount of visible light irradiation exposed to the circular layer of the female mold half (e.g., by controlling the exposure time of chemical irradiation). Subsequently, a subsequent curing step will produce a silicone hydrogel contact lens each comprising a central photochromic zone with a diameter of about 13 mm or less that is concentric with the central axis of the raw hydrogel contact lens.

[0080] The method of the present invention can provide the following benefits. First, the method of the present invention can ensure the physical integrity of the produced hydrogel contact lens. This can also avoid the problem of delamination. In addition, the photochromic functionality is limited to the optical area of ​​the contact lens, that is, the pupil area of ​​the eye when worn. Any color associated with the photochromic functionality would have minimized the negative impact on the aesthetic aspects of the hydrogel contact lens.

[0081] The present invention provides a method for manufacturing a silicone hydrogel contact lens, comprising, in some embodiments, the following steps: (1) obtaining a first polymerizable fluid composition and a second polymerizable fluid composition (the first polymerizable fluid composition comprises at least one free radical initiator, at least one first polymerizable material, and at least one photochromic compound, wherein the at least one polymerizable material has a weight average molecular weight of at least about 5000 daltons (preferably at least about 6000 daltons, more preferably at least about 8000 daltons, more preferably at least about 10000 daltons) and comprises at least one first polysiloxane vinyl crosslinker present in the first polymerizable composition in an amount of at least 40 weight% (preferably at least about 45 weight%, more preferably at least about 50 weight%, more preferably at least about 55 weight%), and the second polymerizable fluid composition comprises the at least one free radical initiator and at least one second polymerizable material and is free of any photochromic compound); (2) a step of obtaining a lens mold comprising a male mold half having a first molding surface defining the rear surface of the contact lens to be molded and a female mold half having a second molding surface defining the front surface of the contact lens to be molded, wherein the female and male mold halves accommodate each other when the mold is closed to form a mold cavity between the first and second molding surfaces; (3) a step of applying a droplet of a first polymerizable fluid composition onto the geometric center of the first molding portion of the male mold half (the volume of the droplet is about 5 μL or less (preferably about 4.5 μL or less, more preferably about 4.0 μL or less, even more preferably about 3.(5 μL or less); (4) dispensing a predetermined amount of a second polymerizable fluid composition onto a second molding surface of a female mold half; (5) closing the female mold half with the male mold half to which the droplet is attached to form a molded assembly comprising droplets of the second polymerizable composition and the first polymerizable composition within the mold cavity; (6) curing the droplets of the second polymerizable fluid composition and the first polymerizable composition to form a raw silicone hydrogel contact lens having a photochromic central region, wherein the photochromic central region has a diameter of about 13 mm or less and is concentric with the central axis of the raw silicone hydrogel contact lens; (7) separating the molded assembly into a male mold half and a female mold half with the raw silicone hydrogel contact lens attached to the lens-attached mold half, which is one of the male and female mold halfs; (8) removing the unprocessed silicone hydrogel contact lens from the lens-attached mold half; and (9) applying the unprocessed silicone hydrogel contact lens to a post-molding process comprising a hydration process and one or more other processes selected from the group consisting of extraction, surface treatment, packaging, sterilization, and combinations thereof.

[0082] Any polymerizable material known or suitable for forming silicone hydrogel contact lenses may be used in the present invention.

[0083] In a preferred embodiment, the at least one first and second polymerizable material is a monomer mixture comprising (a) at least one silicon-containing vinyl monomer, (b) at least one first polysiloxane vinyl crosslinker, at least one second polysiloxane vinyl crosslinker, at least one non-silicon vinyl crosslinker, or a combination thereof, (c) at least one hydrophilic vinyl monomer, (d) at least one free radical initiator, and optionally (e) at least one component selected from the group consisting of a non-silicon hydrophobic vinyl monomer, a UV-absorbing vinyl monomer, a polymerizable UV / HEVL-absorbing compound, and a combination thereof.

[0084] Any silicon-containing vinyl monomer may be used in the present invention. Preferred silicon-containing vinyl monomers may be silicon-containing (meth)acrylamido monomers, silicon-containing (meth)acryloxy monomers, silicon-containing vinylcarbonato monomers, or silicon-containing vinylcarbamato monomers, each of which comprises a bis(trialkylsilyloxy)alkylsilyl group, a tris(trialkylsilyloxy)-silyl group, or a polysiloxane chain having 2 to 30 siloxane units and terminated with an alkyl, hydroxyalkyl, or methoxyalkyl group. Such desirable silicon-containing vinyl monomers may be available from commercial suppliers, or alternatively, vinyl monomers having a reactive functional group (e.g., acid chloride, acid anhydride, carboxyl, hydroxyl, amino, epoxy, isocyanate, aziridine, azlactone, or aldehyde group) may be obtained in accordance with known procedures, e.g., U.S. Patents No. 5070215, No. 6166236, No. 6867245, No. 7214809, No. 8415405, No. 8475529, No. 8614261, No. 8658748, No. 9097840, No. 9103965, No. 9217813, No. 9315669, and No. 9475827, or in accordance with a similar method as described in U.S. Patents No. 5070215, No. 6166236, No. 6867245, No. 7214809, No. 8415405, No. 8475529, No. 8614261, No. 8658748, No. 9097840, No. 9103965, No. 9217813, No. 9315669, and No. 9475827, or in the presence or absence of a coupling agent under coupling reaction conditions well known to those skilled in the art. It can be prepared by reacting with a siloxane-containing compound selected from the group consisting of hydroxyalkyl, aminoalkyl, alkylaminoalkyl, carboxyalkyl, isocyanatoalkyl, epoxyalkyl, and aziridinylalkyl.

[0085] In a preferred embodiment, the at least one silicon-containing vinyl monomer comprises a bis(trialkylsilyloxy)alkylsilyl group, a tris(trialkylsilyloxy)silyl group, or at least one silicon-containing (meth)acrylamido monomer having a polysiloxane chain having 2 to 30 siloxane units and terminated with an alkyl, hydroxyalkyl, or methoxyalkyl group. Examples of such preferred silicon-containing (meth)acrylamido monomers include, but are not limited to, those described below in this application.

[0086] In another preferred embodiment, the at least one silicon-containing vinyl monomer comprises a bis(trialkylsilyloxy)alkylsilyl group, a tris(trialkylsilyloxy)silyl group, or at least one silicon-containing (meth)acryloxy monomer having a polysiloxane chain having 2 to 30 siloxane units and terminated with an alkyl, hydroxyalkyl, or methoxyalkyl group. Examples of such preferred silicon-containing (meth)acryloxy monomers include, but are not limited to, those described below in this application.

[0087] According to the present invention, the at least one first and second polysiloxane vinyl crosslinker may be different from each other and any polysiloxane vinyl crosslinker.Examples of preferred polysiloxane vinyl crosslinkers include α,ω-(meth)acryloxy-terminated polydimethylsiloxane; α,ω-(meth)acrylamido-terminated polydimethylsiloxane; α,ω-vinyl carbonate-terminated polydimethylsiloxane; α,ω-vinyl carbamate-terminated polydimethylsiloxane; bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane; reaction product of glycidyl methacrylate and amino-functional polydimethylsiloxane; reaction product of an azlactone-containing vinyl monomer (any one of those described above) and hydroxyl-functional polydimethylsiloxane; and a polysiloxane-containing macromonomer selected from the group consisting of macromonomer A, macromonomer B, macromonomer C, and macromonomer D as described in US 5,760,100. U.S. Patents No. 4136250, No. 4153641, No. 4182822, No. 4189546, No. 4259467, No. 4260725, No. 4261875, No. 4343927, No. 4254248, No. 4355147, No. 4276402, No. 4327203, No. 4341889, No. 4486577, No. 4543398, No. 4605712, No. 4661575, No. 4684538, No. 4703097, No. 4833218, No. 4837289, No. 4954586, No. 4954587, No. 5010141, No. 5034461, No. 5070170, No. 5079319, No. 5039761, No. 5346946, No. 5358995, No. 5387632, No. 5416132, No. 5449729, No. 5451617, No. 5486579, No. 5962548, No. 5981675, No. 6039913, No. 6762264, No. 7423074, No. 8163206, No. 8480227, No. 8529057, No. 8835525, No. 8993651, No. 9,187,601, No. 10081697, No. 10301451, and It includes, but is not limited to, the polysiloxane vinyl crosslinking agent disclosed in Patent No. 10465047.

[0088] One class of preferred polysiloxane vinyl crosslinkers is a monovalent C4-C having 2 to 6 hydroxyl groups. 40 A di-(meth)acryloyloxy-terminated polysiloxane vinyl crosslinker having a hydrophilized siloxane unit having an organic radical substituent and a dimethylsiloxane unit having a methyl substituent, and more preferably a polysiloxane vinyl crosslinker of formula H, which is described below in this application and can be prepared according to the procedure disclosed in U.S. Patent No. 10081697.

[0089] Another class of preferred polysiloxane vinyl crosslinkers is vinyl crosslinkers (each having one homogeneous polydiorganosiloxane segment and two terminal (meth)acryloyl groups), which may be available from commercial sources; may be prepared by reacting glycidyl (meth)acrylate (meth)acryloyl chloride with di-amino-terminated polydimethylsiloxane or di-hydroxyl-terminated polydimethylsiloxane; may be prepared by reacting isocyanoethyl (meth)acrylate with di-hydroxyl-terminated polydimethylsiloxane; or may be prepared by reacting an amino-containing acrylic monomer with di-carboxyl-terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide); It can be prepared by reacting a carboxyl-containing acrylic monomer with a di-amino-terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide); or it can be prepared by reacting a hydroxyl-containing acrylic monomer with a di-hydroxy-terminated polydisiloxane in the presence of a diisocyanate or a di-epoxy coupling agent.

[0090] Another class of preferred polysiloxane vinyl crosslinkers is a chain-extended polysiloxane vinyl crosslinker having at least two polydiorganosiloxane segments connected by a linker between each pair of two terminal ethylene-based unsaturated groups and a polydiorganosiloxane segment, which can be manufactured according to the procedures described in U.S. Patents No. 5034461, No. 5416132, No. 5449729, No. 5760100, No. 7423074, No. 8529057, No. 8835525, No. 8993651, No. 9187601, No. 10301451, and No. 10465047.

[0091] Any non-silicon vinyl crosslinker may be used in the present invention. Examples of preferred non-silicon vinyl crosslinkers are described below in this application.

[0092] Any hydrophilic vinyl monomer may be used in the present invention. Examples of preferred hydrophilic vinyl monomers include hydrophilic (meth)acrylamido (as described below in this application), hydrophilic (meth)acryloxy monomer (as described below in this application), hydrophilic N-vinylamide monomer (as described below in this application), methylene-containing pyrrolidone monomer (i.e., pyrrolidone derivatives having a methylene group connected to a pyrrolidone ring at the 3- or 5-position, respectively) (as described below in this application), vinyl ether monomer (as described below in this application), allyl ether monomer (as described below in this application), phosphorylcholine-containing vinyl monomer (as described below in this application), allyl alcohol, N-2-hydroxyethyl vinyl carbamate, N-vinyloxycarbonyl-β-alanine (VINAL), N-vinyloxycarbonyl-α-alanine, and combinations of these exist.

[0093] In another preferred embodiment, the one or more hydrophilic vinyl monomers preferably comprise one or more hydrophilic (meth)acrylamido monomers having 3 to 10 carbon atoms. Examples of preferred hydrophilic (meth)acrylamido monomers are described below in this application. It is believed that such hydrophilic (meth)acrylamido monomers can be used to increase the glass transition temperature of the resulting silicon hydrogel material. Additionally, it is understood that any hydrophilic (meth)acrylamido monomer other than those specifically described below in this application may also be used in the present invention.

[0094] In another preferred embodiment, the at least one hydrophilic vinyl monomer comprises at least one hydrophilic N-vinylamide monomer. Examples of preferred hydrophilic N-vinylamide monomers are described below in this application. It is understood that any hydrophilic N-vinylamide monomer other than those specifically described below in this application may also be used in the present invention.

[0095] In another preferred embodiment, the one or more hydrophilic vinyl monomers preferably comprise one or more hydrophilic (meth)acryloxy monomers having 3 to 10 carbon atoms. Examples of preferred hydrophilic (meth)acryloxy monomers are described below in this application. It is understood that any hydrophilic (meth)acryloxy monomer other than those specifically described below in this application may also be used in the present invention.

[0096] In a preferred embodiment, the sum of the amounts of components (a), (b), and (c) in the monomer mixture is about 60% or more (preferably about 65% or more, more preferably about 70% or more, even more preferably about 75% or more) with respect to the total weight of all polymerizable materials in the first polymerizable fluid composition.

[0097] A free radical initiator may be either a photoinitiator or a thermal initiator. "Photoinitiator" refers to a chemical substance that uses light to initiate a free radical crosslinking / polymerization reaction. "Thermal initiator" refers to a chemical substance that uses thermal energy to initiate a free radical crosslinking / polymerization reaction.

[0098] Any free radical photoinitiator may be used in the present invention. Examples of suitable free radical photoinitiators include benzoin methyl ether, diethoxyacetophenone, benzoylphosphine oxide, 1-hydroxycyclohexylphenyl ketone and Darocur and Irgacur types, preferably Darocur 1173® and Darocur 2959®, and germanium-based Norrish type I photoinitiators (e.g., those described in US 7,605,190). Examples of benzoylphosphine initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide; bis-(2,6-dichlorobenzoyl)-4-N-propylphenylphosphine oxide; and bis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide. For example, reactive photoinitiators that can be incorporated into a macromonomer or used as a specific monomer are also suitable. Examples of reactive photoinitiators are those disclosed in EP 632 329.

[0099] In a preferred embodiment, a visible light free radical photoinitiator is used in the present invention. It is believed that irradiation with visible light minimizes decomposition into a photochromic compound. Examples of preferred visible light free radical photoinitiators include, without limitation, acyl germanium photoinitiators, benzoylphosphine oxide, acylphosphinate salts, etc.

[0100] Examples of benzoylphosphine initiators include 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide; bis-(2,6-dichlorobenzoyl)-4-N-propylphenylphosphine oxide; and bis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide. An example of a water-soluble acylphosphine salt is lithium phenyl(2,4,6-trimethylbenzoyl)phosphine, which is commercially available from Tokyo Chemical Industry Co., Ltd.

[0101] Any acyl-germanium photoinitiator may be used in the present invention as long as it can initiate free radical polymerization by irradiating a light source containing light in the range of about 420 to about 500 nm. An example of an acyl-germanium photoinitiator is an acyl-germanium compound described in U.S. Patent No. 7605190. Preferably, the at least one first and / or second free radical initiator comprises at least one of the following acyl-germanium compounds.

[0102] , , and

[0103] Any free radical initiator may be used in the present invention. Suitable free radical initiators are known to those skilled in the art and include, for example, peroxides, hydroperoxides, azo-bis(alkyl- or cycloalkylnitrile), persulfates, percarbonates, or mixtures thereof.Examples of preferred free radical initiators include, without limitation, benzoyl peroxide, t-butyl peroxide, t-amyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexine, bis(1-(tert-butylperoxy)-1-methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di-t-butyl-diperoxyphthalate, t-butyl hydroperoxide, t-butyl peracetate, t-butyl peroxybenzoate, t-butylperoxyisopropyl carbonate, Acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate (Perkadox 16S), di(2-ethylhexyl)peroxydicarbonate, t-butylperoxypivalate (Lupersol 11); t-butylperoxy-2-ethylhexanoate (Trigonox 21-C50), 2,4-pentanedione peroxide, dicumyl peroxide, peracetic acid, potassium persulfate, sodium persulfate, ammonium persulfate, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2'-azobis[2-(2-imidazoline-2-yl)propane]dihydrochloride (VAZO 44), 2,2'-azobis(2-amidinopropane)dihydrochloride (VAZO 50), 2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO 52), 2,2'-azobis(isobutyronitrile) (VAZO 64 or AIBN), 2,2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis(1-cyclohexanecarbonitrile) (VAZO 88); 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(methylisobutyrate), 4,4'-azobis(4-cyanovaleric acid), and combinations thereof are included. Preferably, the thermal free radical initiator is 2,2'-azobis(isobutyronitrile) (AIBN or VAZO 64).

[0104] Any non-silicon hydrophobic vinyl monomer may be used in the present invention. Examples of preferred hydrophobic non-silicon vinyl monomers include non-silicon hydrophobic acrylic monomers (e.g., alkyl (meth)acrylates as described below, cycloalkyl (meth)acrylates as described below, phenyl methacrylate, (meth)acrylonitrile, etc.), and fluorine-containing acrylic monomers (e.g., perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, perfluoro-substituted-C2-C as described below). 12 Alkyl (meth)acrylates, etc.), vinyl alkanoates (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, etc.), vinyloxyalkanes (e.g., vinyl ethyl ether, propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, t-butyl vinyl ether, etc.), substituted or unsubstituted styrenes as described below, vinyl toluene, vinyl chloride, vinylidene chloride, 1-butene, and combinations thereof.

[0105] Any suitable perfluoro-substituted-C2-C 12 Alkyl (meth)acrylates may be used in the present invention. Perfluoro-substituted-C2-C 12 Examples of alkyl (meth)acrylates include, without limitation, 2,2,2-trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoro-iso-propyl (meth)acrylate, hexafluorobutyl (meth)acrylate, heptafluorobutyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, pentafluorophenyl (meth)acrylate, and combinations thereof.

[0106] In a preferred embodiment, one or more hydrophobic non-silicon acrylic monomers and / or substituted or unsubstituted styrenes may be used in the present invention as reactive diluents (i.e., blending vinyl monomers) to dissolve other polymerizable components in the polymerizable composition of the present invention.

[0107] Examples of such non-silicon hydrophobic acrylic monomers and substituted or unsubstituted styrenes include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, phenyl methacrylate, 4-tert-butylstyrene, 2-methylstyrene, styrene, 4-ethoxystyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, and combinations thereof. More preferably, methyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, or combinations thereof are used in the present invention. More preferably, methyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, or a combination thereof is used in the present invention.

[0108] The term "UV / HEVL absorbing vinyl monomer" means a vinyl monomer capable of absorbing UV light and high-energy violet light (i.e., light having a wavelength of 380 nm to 440 nm). Examples of UV absorbing vinyl monomers and UV / HEVL absorbing vinyl monomers are known to those skilled in the art and are disclosed in patents and patent application publications, e.g., US 9315669, US 2018-0081197 A1, etc.

[0109] Any suitable UV-absorbing vinyl monomer and UV / HEVL-absorbing vinyl monomer may be used in the present invention. Examples of preferred UV-absorbing and UV / HEVL-absorbing vinyl monomers include, without limitation, 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-acrylyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-methacrylamidomethyl-5-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-methacryloxypropyl-3'-t-butyl-phenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-5'-methacryloxypropylphenyl). Benzotriazole, 2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazole-2-yl)benzyl methacrylate (WL-1), 2-hydroxy-5-methoxy-3-(5-methoxy-2H-benzo[d][1,2,3]triazole-2-yl)benzyl methacrylate (WL-5), 3-(5-fluoro-2H-benzo[d][1,2,3]triazole-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-2), 3-(2H-benzo[d][1,2,3]triazole-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-3), 3-(5-chloro-2H-benzo[d][1,2,3]triazole-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-4), 2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1,2,3]triazole-2-yl)benzyl methacrylate (WL-6), 2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazole-2-yl)benzyl methacrylate (WL-7), 4-allyl-2-(5-chloro-2H-benzo[d][1,2,3]triazole-2-yl)-6-methoxyphenol (WL-8), 2-{2'-hydroxy-3'- tert -5'[3"-(4"-vinylbenzyloxy)propoxy]phenyl}-5-methoxy- 2H -Benzotriazole, phenol, 2-(5-chloro-2H -benzotriazole-2-yl)-6-(1,1-dimethylethyl)-4-ethenyl- (UVAM), 2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole (2-propenic acid, 2-methyl-, 2-[3-(2 H -benzotriazole-2-yl)-4-hydroxyphenyl]ethyl ester, Norbloc), 2-{2'-hydroxy-3'- tert -butyl-5'-[3'-methacryloyloxypropoxy]phenyl}- 2H -Benzotriazole, 2-{2'-hydroxy-3'- tert -butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-methoxy- 2H -Benzotriazole (UV13), 2-{2'-hydroxy-3'- tert -butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-chloro- 2H -Benzotriazole (UV28), 2-[2'-hydroxy-3'- tert -butyl-5'-(3'-acryloyloxypropoxy)phenyl]-5-trifluoromethyl- 2H -Benzotriazole (UV23), 2-(2'-hydroxy-5-methacrylamidophenyl)-5-methoxybenzotriazole (UV6), 2-(3-allyl-2-hydroxy-5-methylphenyl)- 2H -Benzotriazole (UV9), 2-(2-hydroxy-3-metallyl-5-methylphenyl)- 2H -Benzotriazole (UV12), 2-3'-t-butyl-2'-hydroxy-5'-(3"-dimethylvinylsilylpropoxy)-2'-hydroxy-phenyl)-5-methoxybenzotriazole (UV15), 2-(2'-hydroxy-5'-methacryloylpropyl-3'-tert-butyl-phenyl)-5-methoxy- 2H -Benzotriazole (UV16), 2-(2'-hydroxy-5'-acryloylpropyl-3'-tert-butyl-phenyl)-5-methoxy- 2H-Benzotriazole (UV16A), 2-methylacrylic acid 3-[3-tert-butyl-5-(5-chlorobenzotriazole-2-yl)-4-hydroxyphenyl]-propyl ester (16-100, CAS#96478-15-8), 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazole-2-yl)phenoxy)ethyl methacrylate (16-102); phenol, 2-(5-chloro-2 H -benzotriazole-2-yl)-6-methoxy-4-(2-propene-1-yl) (CAS#1260141-20-5); 2-[2-hydroxy-5-[3-(methacryloyloxy)propyl]-3- tert -butylphenyl]-5-chloro-2 H -Benzotriazole; phenol, 2-(5-ethenyl-2H-benzotriazole-2-yl)-4-methyl-, homopolymer (9CI) (CAS#83063-87-0) is included. According to the present invention, the polymerizable composition comprises one or more UV-absorbing vinyl monomers in an amount of about 0.1% to about 3.0% by weight, preferably about 0.2% to about 2.5% by weight, more preferably about 0.3% to about 2.0% by weight, with respect to the amount of all polymerizable components in the polymerizable composition.

[0110] The first and second polymerizable fluid compositions of the present invention may also include other essential components known to those skilled in the art, examples thereof as known to those skilled in the art, such as a visibility coloring agent (e.g., one or more polymerizable dyes, pigments, or mixtures thereof), an antimicrobial agent (e.g., silver nanoparticles), a bioactive agent (e.g., drugs, amino acids, polypeptides, proteins, nucleic acids, 2-pyrrolidone-5-carboxylic acid (PCA), alpha hydroxylic acids, linoleic acid and gamma linoleic acid, vitamins, or combinations thereof), an leaching lubricant (e.g., a non-crosslinked hydrophilic polymer having an average molecular weight of 5,000 to 500,000, preferably 10,000 to 300,000, more preferably 20,000 to 100,000 daltons), and an leaching tear stabilizer (e.g., phospholipids, monoglycerides, diglycerides, triglycerides, glycolipids, There are glyceroglycolipids, sphingolipids, sphingoglycolipids, fatty acids having 8 to 36 carbon atoms, fatty alcohols having 8 to 36 carbon atoms, or mixtures thereof), release agents and mixtures thereof.

[0111] According to the present invention, the first and second polymerizable fluid compositions of the present invention may be solutions or solvent-free blends (i.e., fluid compositions without any non-reactive diluent-organic solvent). These may also be prepared according to any technique known to those skilled in the art.

[0112] The first or second polymerizable fluid composition of the present invention may also be prepared from any known silicone hydrogel lens formulation. For example, the first polymerizable fluid composition may be prepared by adding at least one photochromic compound and at least one first polysiloxane vinyl crosslinking agent to any one of the known silicone hydrogel (SiHy) lens formulations, whereas the second polymerizable fluid composition may be any one of the known SiHy lens formulations.

[0113] Numerous SiHy lens formulations have been described in numerous patents and patent applications disclosed up to the filing date of this application and have been used to manufacture commercially available SiHy contact lenses. Examples of commercially available SiHy contact lenses include, without limitation, asmofilcon A, balafilcon A, comfilcon A, delefilcon A, efrofilcon A, enfilcon A, fanfilcon A, galyfilcon A, lotrafilcon A, lotrafilcon B, narafilcon A, narafilcon B, senofilcon A, senofilcon B, senofilcon C, smafilcon A, somofilcon A, and stenfilcon A.

[0114] If the first or second polymerizable fluid composition of the present invention is a solution, it may be prepared by dissolving all desirable components in any suitable solvent known to those skilled in the art. Examples of suitable solvents include, without limitation, water, tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone, methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, polyethylene glycol, polypropylene glycol, and ethyl Acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, i-propyl lactate, methylene chloride, 2-butanol, 1-propanol, 2-propanol, methanol, cyclohexanol, cyclopentanol and exonorborneol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 3-octanol, norborneol, tert-butanol, tert-amyl alcohol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol, 1-methylcyclohexanol, 2-methyl-2-hexanol, 3,7-dimethyl-3-octanol, 1-chloro-2-methyl-2-propanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, 2-2-methyl-2-nonanol, 2-methyl-2-decanol, 3-methyl-3-hexanol, 3-methyl-3-heptanol, 4-methyl-4-heptanol, 3-methyl-3-octanol, 4-methyl-4-octanol, 3-methyl-3-nonanol, 4-methyl-4-nonanol, 3-methyl-3-octanol, 3-ethyl-3-hexanol, 3-methyl-3-heptanol,4-ethyl-4-heptanol, 4-propyl-4-heptanol, 4-isopropyl-4-heptanol, 2,4-dimethyl-2-pentanol, 1-methylcyclopentanol, 1-ethylcyclopentanol, 1-ethylcyclopentanol, 3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1-cyclopentanol, 2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol, 2,3,4-trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol, 2-methyl-1-phenyl-2-propanol, and 3-ethyl-3-pentanol, 1-ethoxy-2-propanol, 1-methyl-2-propanol, t-amyl alcohol, isopropanol, 1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, dimethylformamide, dimethylacetamide, dimethylpropionamide, N-methylpyrrolidinone, and mixtures thereof are included. Preferably, the polymerizable composition is a solution of all preferred components among water, 1,2-propylene glycol, polyethylene glycol having a molecular weight of about 400 daltons or less, or a mixture thereof.

[0115] If the first or second polymerizable fluid composition of the present invention is a solvent-free blend, it may be prepared by mixing all polymerizable components and other necessary components. The solvent-free polymerizable composition generally comprises at least one blending vinyl monomer as a reactive solvent for dissolving all other polymerizable components of the solvent-free polymerizable composition. Examples of preferred blending vinyl monomers are described above and below in this application. Preferably, methyl methacrylate is used as the blending vinyl monomer in the preparation of the solvent-free polymerizable composition.

[0116] Any polymerizable photochromic compound may be used in the present invention. Examples of preferred polymerizable photochromic compounds include polymerizable naphtopyran, polymerizable benzopyran, polymerizable indenonaphtopyran, polymerizable phenantropyran, as disclosed in U.S. Patents No. 4929693, 5166345, 6017121, 7556750, 7584630, 7999989, 8158037, 8697770, 8741188, 9052438, 9097916, 9465234, 9904074, 10197707, 6019914, 6113814, 6149841, 6296785, and 6348604. Polymerizable spiro(benzindoline)-naphtopyran, polymerizable spiro(indoline)benzopyran, polymerizable spiro(indoline)-naphtopyran, polymerizable spiro(indoline)quinopyran, polymerizable spiro(indoline)-pyran, polymerizable naphthoxazine, polymerizable spirobenzopyran; polymerizable spirobenzopyran, polymerizable spirobenzothiopyran, polymerizable naphthacendione, polymerizable spirooxazine, polymerizable spiro(indoline)naphthoxazine, polymerizable spiro(indoline)pyridobenzoxazine, polymerizable spiro(benzindoline)pyridobenzoxazine, polymerizable spiro(benzindoline)naphthoxazine, polymerizable spiro(indoline)benzoxazine, polymerizable spiro(indoline)benzoxazine, polymerizable dialylethene, and combinations thereof are included.

[0117] Various photochromic compounds are disclosed in patents and published patent applications and can be obtained from commercial sources or manufactured according to procedures described in patents and literature. Examples of preferred photochromic compounds include, without limitation, naphtopyran, indeno-fused naphtopyran (i.e., indeno-naphtopyran), heterocyclic ring-fused naphtopyran, benzopyran, phenantropyran, quinopyran, quinolinopyran, fluoroantenopyran, anthracene-fused pyran, tetracene-fused pyran, spiro(benzindolin)naphtopyran, spiro(indolin)naphtopyran, spiro(indolin)benzopyran, spiro(indolin)quinopyran, spiro(indolin)pyran, naphthoxazine, spirobenzopyran, spirobenzothiopyran, naphthacenedione, benzoxazine, spirooxazine, naphthoxazine, spiro(benzindolin)naphthoxazine, spiro(indolin)naphthoxazine, spiro(indolin)pyrido-benzoxazine. Spiro(Indoline) Benzocecone, Spiro(Benzindolin) Benzocecone, Spiro(Benzindolin)Pyridobenzocecone, Spiro(Indoline)Fluoranthenoxocecone, Spiro(Indoline)-Quinoxocecone, Spiropiperidine-Naphtophyran, Pyro(Indoline)Pyronovencoce, Benzospiropyran, Naphthospiropyran, Spirobenzocecone-Pyrrolopyridine, Spironaftok-Pyrrolopyridine, Spiro-Oxazepine-Benzocecone, Spiro-Oxazepine-Naphtokecone, Spiro(Indoline)Benzothiazolocecone, Spiro(Indoline)Benzopyrolocecone, Spiro(Indoline)Quinazolino-Oxocecone, Spiro(Indoline)Anthracenobenzocecone, Benzofuro-Benzopyran, Benzothienobenzopyran, These include naphthofurobenzopyran, benzopyrano-fused naphthofyran, spiro(isoindoline)-naphtoxane, spiro(isoindoline)benzoxane, etc. These photochromic compounds are U.S. Patents No. 3100778, No. 3562172, No. 3567605, No. 3578602, No. 3671543, No. 4215010, No. 4342668, No. 4440672, No. 4634767, No. 4636561, No. 4637698, No. 4699473, No. 4719296, No. 4720547, No. 4772700, No. 4784474, No. 4785097, No. 4816584, No. 4818096,No. 4826977, No. 4831142, No. 4880667, No. 4929693, No. 4931219, No. 4931221, No. 4959471, No. 4980089, No. 4986934, No. 5055576, No. 5066818, No. 5110922, No. 5114621, No. 5139707, No. 5166345, No. 5171636, No. 5180524, No. 5186867, No. 5200116, No. 5238931, No. 5238981, No. 5244602, No. 5274132, No. 5340857, No. 5369158, No. 5384077, No. 5395567, No. 5399687, No. 5405958, No. 5411679, No. 5429774, No. 5451344, No. 5458814, No. 5458815, No. 5464567, No. 5466398, No. 5514817, No. 5520853, No. 5552090, No. 5552091, No. 5565147, No. 5573712, No. 5578252, No. 5585042, No. 5623005, No. 5637262, No. 5637709, No. 5645767, No. 5650098, No. 5651923, No. 5656206, No. 5658500, No. 5658501, No. 5674432, No. 5698141, No. 5723072, No. 5728758, No. 5730908, No. 5744070, No. 5759450, No. 5783116, No. 5801243, No. 5808063, No. 5811034, No. 5831090, No. 5833885, No. 5869658, No. 5879592, No. 5891368, No. 5955520, No. 5961892, No. 5981634, No. 5998520, No. 6004486, No. 6017121, No. 6018059, No. 6019914, No. 6022495, No. 6022497, No. 6030555, No. 6034193, No. 6065836, No. 6106744, No. 6106744, No. 6107395, No. 6113814, No. 6146554, No. 6149841, No. 6153126, No. 6221284, No. 6248264,No. 6296785, No. 6315928, No. 6342459, No. 6348604, No. 6353102, No. 6414057, No. 6478988, No. 6630597, No. 7556750, No. 7584630, No. 7999989, No. 8158037, No. 8697770, No. 8698117, No. 8741188, No. 9029532, No. 9028728, No. 9052438, No. 9097916, No. 9465234, No. 9487499, No. 9904074, No. 10197707, No. 10501446, Disclosed in Patent No. 10532997 and No. 10502998, and also described in the literature [Techniques in Chemistry, Volume III. “Photochromism”, Chapter 3 (Glenn H. Brown, Editor, John Wiley and Sons, Inc., New York, 1971) and “Chromic Phenomena: Technological Applications of Colour Chemistry” (P. Bamfield, RSC Books (2001))]. Derivatives of these compounds containing various substituents can be synthesized from this teaching by those skilled in the art.

[0118] A polymerizable photochromic compound, under well-known coupling reaction conditions, in the absence or presence of a coupling agent (i.e., having two of the reactive functional groups listed above), has a first reactive functional group (-COCl, -COBr, -COOH, -NHR). N2 , -NCO, -OH, -CHO, , , or , where R0 is hydrogen or methyl and R N2 is hydrogen, linear or branched C1-C 15A reactive (meth)acrylamido or (meth)acryloxy monomer having an alkyl, cyclohexyl, cyclopentyl, substituted or unsubstituted phenyl, or substituted or unsubstituted phenyl-C1-C6 alkyl group, and a second reactive functional group (-COOH, -NHR). N2 , , , , -NCO, -OH, -SH, -CHO, , , or It can be obtained by reacting with a reactive photochromic compound having ) to form a photochromic compound.

[0119] Preferably, non-limiting examples of coupling reactions under various reaction conditions between a pair of matching co-reactive functional groups selected from the group consisting of primary groups, secondary amino groups, hydroxyl groups, carboxyl groups, acid anhydride groups, aldehyde groups, isocyanate groups, epoxy groups, aziridine groups, azlactone groups, and thiol groups are provided below for exemplary purposes. The primary / secondary amino group reacts with an aldehyde or ketone group to form a Schiff base that can be further reduced to an amine bond; the primary / secondary amino group -NHR (where R is hydrogen or C1-C6 alkyl) reacts with an acid chloride or bromide group or with an acid anhydride group to form an amide linkage (-CO-NR-); the amino group -NHR reacts with an N-hydroxysuccinimide ester group to form an amide linkage; The amino group -NHR reacts with a carboxylic acid group in the presence of a coupling agent - carbodiimide (e.g., 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), N,N'-dicyclohexylcarbodiimide (DCC), 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide, diisopropylcarbodiimide, or a mixture thereof) and N-hydroxysuccinimide to form an amide linkage; the amino group -NHR reacts with an azlactone group (ring-opening) to form an alkylene-diamido linkage (-CONH-CR 1 R 2-(CH2) p1 -CONH-) forms; the amino group -NHR reacts with the isocyanate group to form a urea linkage (-NR-C(O)-NH-(R is as defined above)); the amino group -NHR reacts with the epoxy or aziridine group to form an amine linkage (-C-NR-); the hydroxyl group reacts with the isocyanate to form a urethane linkage; the hydroxyl group reacts with the epoxy or aziridine to form an ether linkage (-O-); the hydroxyl group reacts with the acid chloride or bromide group or with the acid anhydride group to form an ester linkage; the carboxyl group reacts with the epoxy group to form an ester linkage; the thiol group (-SH) reacts with the isocyanate to form a thiocarbamate linkage (-NC(O)-S-); the thiol group reacts with the epoxy or aziridine to form a thioether linkage (-S-); The thiol group reacts with acid chloride or bromide groups or with acid anhydride groups to form a thioester linkage; the thiol group reacts with azlactone groups in the presence of a catalyst to form a linkage (-CONH-CR 1 R 2 -(CH2) p1 -CO-S-) forms; the thiol group reacts with the en group or vinylsulfonyl group based on the thiol-en "click" reaction under thiol-en reaction conditions to form the thioether link (-S-); the thiol group reacts with the (meth)acryloyl group based on Michael Addition under appropriate reaction conditions to form the thioether link.

[0120] The reaction conditions for the aforementioned coupling reaction are taught in textbooks and are well known to those skilled in the art.

[0121] Any coupling agent having two reactive functional groups may be used in the coupling reaction. Coupling agents having two reactive functional groups may be as follows: diisocyanate compounds; di-acid halide compounds; di-carboxylic acid compounds; di-carboxylic acid anhydride compounds; diamine compounds; diol compounds; di-epoxy compounds; di-aziridine compounds; di-azlactone compounds; di-ene compounds; divinylsulfone compounds; di-thiol compounds; thiolactone compounds; amino acid compounds; hydroxy-containing amine compounds; amine compounds having one hydroxyl or ketone group; hydroxy-containing carboxylic acid compounds; mercaptans having a hydroxyl, carboxyl, or amino group.

[0122] For example, diisocyanate, dicarboxylic acid (preferably dicarboxylic acid anhydride), diaziridine, diepoxy, or diazolactone compounds may be used for coupling the first and second reactive functional groups (where they are different or the same and selected from the group consisting of hydroxyl, primary amino, secondary amino, and thiol groups); diamine, dihydroxyl, dithiol, hydroxy-containing amine, or hydroxy-containing thiol compounds may be used for coupling the first and second reactive functional groups (where they are different or the same and selected from the group consisting of isocyanate, epoxy, aziridine, and carboxylic acid groups); and diepoxy compounds may be used for coupling the first and second reactive functional groups (where both are carboxylic acid groups); Diamine compounds may be used for coupling the first and second reactive functional groups (where both are aldehyde groups). Those skilled in the art are well aware of a method for forming the photochromic polydioganosiloxane vinyl crosslinker of the present invention by selecting one or more coupling agents based on the selectivity and / or differential reactivity of a given reactive functional group to link the first and second reactive functional groups.

[0123] Examples of commercially available dicarboxylic acid anhydrides include, without limitation, succinic anhydride, methyl succinic anhydride, 2,2-dimethyl succinic anhydride, 2,3-dimethyl succinic anhydride, glutaric anhydride, 3,3-dimethyl glutaric anhydride, 2,2-dimethyl glutaric anhydride, 3-methyl glutaric anhydride, 3,3-tetramethyl glutaric anhydride, diglycolic anhydride, adipic anhydride, etc.

[0124] Any suitable C3-C 24 Dicarboxylic acid compounds may be used in the present invention. Preferred examples of dicarboxylic acid compounds include, without limitation, linear or branched C3-C 24 Aliphatic dicarboxylic acid, C5-C 24 cycloaliphatic or aliphatic-cycloaliphatic dicarboxylic acid, C6-C 24 Includes aromatic or ar aliphatic dicarboxylic acids, dicarboxylic acids containing an amino or imido group or an N-heterocyclic ring, and combinations thereof. Examples of suitable aliphatic dicarboxylic acids are as follows: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, souveric acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, dimethylmalonic acid, octadecyl succinic acid, trimethyladipic acid, and dimeric acids (dimerization products of unsaturated aliphatic carboxylic acids such as oleic acid). Examples of suitable cycloaliphatic dicarboxylic acids are as follows: 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4-dicarboxymethylcyclohexane, 4,4'-dicyclohexyldicarboxylic acid. Examples of suitable aromatic dicarboxylic acids are as follows: terephthalic acid, isophthalic acid, o-phthalic acid, 1,3-, 1,4-, 2,6-, or 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyl-dicarboxylic acid, 4,4'-diphenylsulfone-dicarboxylic acid, 1,1,3-trimethyl-5-carboxyl-3-(p-carboxyphenyl)-indane, 4,4'-diphenyl ether-dicarboxylic acid, bis-p-(carboxyphenyl)-methane.

[0125] Any suitable diacid halide may be used in the present invention. Preferred examples of diacid halides include, but are not limited to, fumaryl chloride, suberoyl chloride, succinyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, sebacoyl chloride, adipoyl chloride, trimethyladipoyl chloride, azelaoil chloride, dodecandioic acid chloride, succin chloride, glutaric acid chloride, oxalyl chloride, dimeric acid chlorides, and combinations thereof.

[0126] Any suitable diamine may be used in the present invention. Organic diamines are linear or branched C2-C 24 Aliphatic diamine, C5-C 24 cycloaliphatic or aliphatic-cycloaliphatic diamines, or C6-C 24It may be an aromatic or alkyl-aromatic diamine. Preferred organic diamines are N,N'-bis(hydroxyethyl)ethylenediamine, N,N'-dimethylethylenediamine, ethylenediamine, N,N'-dimethyl-1,3-propanediamine, N,N'-diethyl-1,3-propanediamine, N-methyl-1,3-diaminopropane, N-methylethylenediamine, N-ethylethylenediamine, N-isopropyl-1,3-propanediamine, N-propyl-1,3-propanediamine, N-butylethylenediamine, 2,2-dimethyl-1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, hexamethylenediamine, 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine, N,N'-dimethyl-1,6-hexamethylenediamine, 2, 2,4(2,4,4)-trimethyl-1,6-hexanediamine, 1,3-diamino-2-propanol, 1,2-diaminoethane-1,2-diol, 1,1-diaminoethane-1,2-diol, 1,4-diamino-2,3-butanediol, 1,3-cyclopentanediamine, 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclohexylamine), isophorone diamine (3-aminomethyl-3,5,5-trimethylcyclohexylamine), m-xylylene diamine, p-xylylene diamine, piperazine, 1-(2-aminoethyl)piperazine, 1,4-bis(3-aminopropyl)piperazine, These include 2-piperazinoethylamine, 1-Boc-piperazine, 4-(2-aminoethyl)-1-Boc-piperazine, 1-(2-N-Boc-aminoethyl)piperazine, 4-(2-aminoethyl)-1-Boc-piperazine, 4-aminopiperidine, 3-aminopiperidine, 4-aminomethylpiperidine, 2-aminomethylpiperidine, 1-Boc-piperidine-4-carboxaldehyde, 1-Boc-piperidine-4-acetaldehyde, etc.

[0127] Any suitable C4-C 24Diisocyanates may be used in the present invention. Preferred examples of diisocyanates include, without limitation, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, 1,6-diisocyanato-2,2,4-trimethylhexane, octamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane diisocyanate, 1,3-bis-(4,4'-isocyanotomethyl)cyclohexane, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, toluene diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, p-phenylene isocyanate, etc.

[0128] Any suitable di-epoxy compound may be used in the present invention. Examples of preferred di-epoxy compounds include neopentyl glycol diglycidyl ether, 1,3-butadiene diepoxide, 1,4-butanediol diglycidyl ether, 1,2,7,8-diepoxyoctane, 3,4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, vinylcyclohexene dioxide, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, There are bis[4-(glycidyloxy)phenyl]methane, bisphenol A diglycidyl ether (2,2-bis[4-(glycidyloxy)phenyl]-propane), bisphenol A propoxylate diglycidyl ether, and combinations thereof.

[0129] Any suitable C2-C 24Diols (i.e., compounds having two hydroxyl groups) may be used in the present invention. Preferred examples of diols include, without limitation, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,4-butanediol, various pentanediols, various hexanediols, various cyclohexanediols, 1,4-bis(2-hydroxyethyl)piperazine, bisphenol A, bisphenol F, 4,4'-methylenediphenol, and combinations thereof.

[0130] Any amino acid may be used in the present invention. Examples of amino acids include, without limitation, glycine, proline, alanine, valine, isoleucine, leucine, 2-aminoisobutyric acid, 4-aminobutyric acid, 3-aminoisobutyric acid, 3-amino-butyric acid, β-alanine, 1-amino-3-cyclopentane carboxylic acid, 3-aminocyclohexane carboxylic acid, pyrrolidine-3-carboxylic acid, 4-piperidine carboxylic acid, 3-piperidine carboxylic acid, 1-piperazine acetic acid, etc.

[0131] Examples of compounds having one amino group and one hydroxyl or aldehyde group (or ketone group) are, without limitation, 1-piperazinepropanol, 2-[2-(1-piperazinyl)ethoxy]-ethanol, 4-amino-1-piperazineethanol, 4-piperidinemethanol, 1-Boc-piperidine-4-carboxaldehyde, 4-formylpiperidine, N-Boc-4-piperidineacetaldehyde, etc.

[0132] Desirable reactive (meth)acrylamido or (meth)acryloxy monomers include, without limitation, those described below in this application.

[0133] Desired photochromic compounds include, without limitation, compounds that are described below in this application and can be obtained from commercial suppliers, or compounds that can be manufactured according to the patent discussed above and the procedures described in the text above.

[0134] Lens molds for manufacturing contact lenses, including hydrogel contact lenses, are well known to those skilled in the art and are used, for example, in cast molding or spin casting. For example, a mold (for cast molding) generally comprises at least two mold sections (or parts) or mold halves, namely a first and a second mold halve. The first mold halve defines a first molding (or optical) surface and the second mold halve defines a second molding (or optical) surface. The first and second mold halves are configured to receive each other to form a lens-forming cavity between the first molding surface and the second molding surface. The molding surface of the mold halve is the cavity-forming surface of the mold and is in direct contact with the polymerizable composition.

[0135] Methods for manufacturing mold sections for casting contact lenses are generally well known to those skilled in the art. The method of the present invention is not limited to any specific mold forming method. In fact, any mold forming method may be used in the present invention.

[0136] Generally, the mold consists of at least two mold halves (or mold sections), one male mold half and one female mold half. The male mold half has a first molding (or optical) surface that is in direct contact with the polymerizable composition for casting a contact lens and defines the rear (concave) surface of the molded contact lens; the female mold half has a second molding (or optical) surface that is in direct contact with the polymerizable composition and defines the front (convex) surface of the molded contact lens. The male and female mold halves are configured to receive each other to form a lens forming cavity between the first molding surface and the second molding surface.

[0137] Mold half can be formed through various techniques such as injection molding. Methods for manufacturing mold half for cast-molding contact lenses are generally well known to those skilled in the art. The method of the present invention is not limited to any specific mold forming method. In fact, any mold forming method may be used in the present invention. The first and second mold half can be formed through various techniques such as injection molding or lathing. Examples of processes suitable for forming mold half are disclosed in U.S. Patents No. 4444711; No. 4460534; No. 5843346; and No. 5894002.

[0138] Almost all materials known in the art for mold manufacturing can be used to manufacture molds for contact lens manufacturing. For example, polymeric materials, such as polyethylene, polypropylene, polystyrene, PMMA, and Topas ® COC grade 8007-S10 (a transparent amorphous copolymer of ethylene and norbornene from Ticona GmbH in Frankfurt, Germany and Summit in New Jersey, USA) may be used. Other materials that allow UV light transmission, such as quartz glass and sapphire, may be used.

[0139] According to the present invention, the first or second polymerizable fluid composition can be distributed onto the molding surface of a female mold half according to any known technique.

[0140] A specific amount of the second polymerizable fluid composition is generally distributed into the female mold half by a dispensing device, then the male mold half is raised and the mold is closed. As the mold is closed, any excess of the second polymerizable fluid composition is compressed into an overflow provided in the female mold half (or alternatively the male mold half).

[0141] A molded assembly (i.e., a closed mold containing droplets of the second polymerizable fluid composition and the first polymerizable fluid composition) is then heat-cured (i.e., by heating) or chemically-cured (i.e., chemical radiation, e.g., UV radiation and / or visible light) to activate a free radical initiator as known to those skilled in the art, thereby producing a molded, unprocessed silicone hydrogel contact lens.

[0142] Chemical curing of the first and second polymerizable fluid compositions in the molded assembly can be performed by irradiating the closed molded assembly with UV or visible light according to any technique known to those skilled in the art.

[0143] According to the present invention, any visible light may be used in the partial curing step. Preferably, visible light in the 420 nm to 500 nm range is used in the present invention. The light source may be any that emits light in the 420 to 500 nm range sufficient to activate the acyl-germanium photoinitiator. Blue light sources are commercially available and include: the Palatray Cu Blue-Light Unit (available from Heraeus Kulzer, Inc., Irvine, Calif.), the Fusion F450 blue light system (available from TEAMCO, Richardson, Tex.), the Dymax Blue Wave 200, Opsytec's LED light source (435 nm, 445 nm, 460 nm), and the GE 24" blue fluorescent lamp (available from General Electric Company, US). A preferred blue light source is Opsytec's LED (as described above).

[0144] The thermal curing (i.e., polymerization) of droplets of the second polymerizable fluid composition and the first polymerizable fluid composition within the molded assembly can be conveniently carried out in an oven at a temperature of 25 to 120°C, preferably 40 to 100°C, as is well known to those skilled in the art. The reaction time may vary within a wide range, but conveniently, for example, 1 to 24 hours or preferably 2 to 12 hours. It is advantageous to degas the silicone-hydrogel-lens-forming composition beforehand and carry out the copolymerization reaction under an inert atmosphere, for example, under an N2 or Ar atmosphere.

[0145] After curing, the mold can also be opened according to any technique known to those skilled in the art. After the mold is separated, the molded raw silicone hydrogel contact lens is attached to one of the male and female mold halves.

[0146] An unprocessed silicone hydrogel contact lens attached to a lens-attached mold half may undergo one or more post-molding processes after being removed from the lens-attached mold half.

[0147] For example, an unprocessed silicone hydrogel contact lens can be extracted with a liquid extraction medium to remove unpolymerized polymerizable components and formed oligomers. According to the present invention, the extraction liquid medium is an organic solvent, any solvent capable of dissolving unpolymerized polymerizable material and oligomers in a dry contact lens. Water, any organic solvent known to those skilled in the art, or a mixture thereof may be used in the present invention. Preferably, the organic solvent used as the extraction liquid medium is water, buffered brine, C1-C3 alkyl alcohol, 1,2-propylene glycol, polyethylene glycol having a number average molecular weight of about 400 daltons or less, C1-C6 alkyl alcohol, or a combination thereof.

[0148] The hydrogel contact lens may also be packaged in a lens package with a packaging solution that may contain, for example, a surface treatment (e.g., plasma treatment, chemical treatment, grafting of hydrophilic monomers or macromonomers onto the lens surface, layer-by-layer coating, in-package crosslinking of a thermally reactive hydrophilic polymer material, etc.); about 0.005 wt% to about 5 wt% of a wetting agent (e.g., hydrophilic polymer), a viscosity enhancer (e.g., methylcellulose (MC), ethyl cellulose, hydroxymethylcellulose, hydroxyethyl cellulose (HEC), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC), or a mixture thereof), or an in-package coating material; and may undergo additional processes such as sterilization, such as an autoclave, at 118 to 124°C for at least about 30 minutes.

[0149] Preferred surface treatments include LbL coatings as disclosed in U.S. Patents No. 6451871, 6719929, 6793973, 6811805, and 6896926, plasma treatment, and in-package coatings as disclosed in U.S. Patents No. 8557334, 8529057, and 9505184. Preferred plasma treatment is a process in which an ionized gas is applied to the surface of an article, as described in U.S. Patents No. 4312575 and 4632844.

[0150] Hydrogel contact lenses are hydrated in water or an aqueous solution to replace the liquid extraction medium according to any method known to those skilled in the art.

[0151] Hydrated and / or surface-treated photochromic contact lenses may undergo additional processes such as packaging within a lens package having a packaging solution well known to those skilled in the art, for example; sterilization such as autoclaving at 118 to 124°C for about 30 minutes or more.

[0152] Lens packages (or containers) for autoclaving and storing soft contact lenses are well known to those skilled in the art. Any lens package may be used in the present invention. Preferably, the lens package is a blister package comprising a base and a cover, the cover being removablely sealed to the base, and the base comprising a cavity for receiving a sterile packaging solution and a contact lens.

[0153] Lenses are packaged into individual packages, sealed, and sterilized (e.g., by autoclave at about 120°C or higher under pressure for at least 30 minutes) before being distributed to users. Those skilled in the art will understand well how to seal and sterilize lens packages.

[0154] The oxygen permeability of the SiHy contact lens of the present invention is preferably about 40 barrer or more (at about 35°C), more preferably about 60 barrer or more, and even more preferably about 80 barrer or more.

[0155] The elastic modulus of the hydrogel contact lens of the present invention is about 1.5 MPa or less (at a temperature of about 22°C to 28°C), preferably about 1.2 MPa or less, more preferably about 0.3 MPa to about 1.0 MPa.

[0156] The hydrogel contact lens of the present invention further has an equilibrium water content of about 15% to about 75% (at room temperature) when fully hydrated, more preferably about 20% to about 70 wt%, and more preferably about 25% to about 65 wt%. The equilibrium water content of the photochromic contact lens can be measured according to the procedure disclosed in Example 1.

[0157] In a further embodiment, the present invention provides a hydrogel contact lens obtained according to the method of the present invention.

[0158] All various embodiments of the mold, polymerizable composition, radiation spatial limitation, and contact lens of the present invention described above may be used in this aspect of the present invention.

[0159] Although various embodiments of the present invention have been described using specific terms, devices, and methods, such description is for illustrative purposes only. The words used are descriptive, not limiting. It should be understood that modifications and variations may be made by those skilled in the art without departing from the spirit or scope of the invention as set forth in the following claims. Furthermore, it should be understood that aspects of various embodiments may be interchangeable in whole or in part, or may be combined and / or used together in any manner as exemplified below:

[0160] 1. A method for manufacturing a hydrogel contact lens,

[0161] (1) A step of obtaining a first polymerizable fluid composition and a second polymerizable fluid composition (the first polymerizable fluid composition comprises at least one first free radical initiator, at least one first polymerizable material, and at least one photochromic compound, wherein the at least one first polymerizable material comprises at least one first polysiloxane vinyl crosslinker having a weight average molecular weight of at least 5000 daltons and present in the first polymerizable composition in an amount of at least 40 weight%, and the second polymerizable fluid composition comprises at least one second free radical initiator and at least one second polymerizable material and is free of any photochromic compound);

[0162] (2) A step of obtaining a lens mold comprising a male mold half having a first molding surface defining the rear surface of a contact lens to be molded and a female mold half having a second molding surface defining the front surface of a contact lens to be molded, wherein when the mold is closed, the female and male mold halves accommodate each other to form a mold cavity between the first and second molding surfaces;

[0163] (3) A step of applying a droplet of the first polymerizable fluid composition onto the geometric center of the first molding portion of the water mold half (the volume of the droplet is about 5 μL or less);

[0164] (4) A step of distributing a predetermined amount of a second polymerizable fluid composition onto a second molding surface of a female mold half;

[0165] (5) A step of closing the female mold half with the male mold half to which the droplets are attached to form a molded assembly comprising droplets of the second polymerizable composition and the first polymerizable composition within the mold cavity;

[0166] (6) A step of curing droplets of the second polymerizable fluid composition and the first polymerizable composition to form a raw silicone hydrogel contact lens having a photochromic central region, wherein the photochromic central region has a diameter of about 13 mm or less and is concentric with the central axis of the raw silicone hydrogel contact lens;

[0167] (7) A step of separating the molded assembly into a male mold half and a female mold half, with an unprocessed silicone hydrogel contact lens attached to one of the male and female mold halfs, the lens-attached mold half;

[0168] (8) a step of removing the unprocessed silicone hydrogel contact lens from the lens-attached mold half; and

[0169] (9) A step of applying an unprocessed silicone hydrogel contact lens to a post-molding process comprising a hydration process and one or more other processes selected from the group consisting of extraction, surface treatment, packaging, sterilization, and combinations thereof.

[0170] A method including

[0171] 2. A method according to Embodiment 1, wherein at least one first polysiloxane vinyl crosslinking agent has a weight average molecular weight of about 6,000 daltons or more.

[0172] 3. A method according to Embodiment 2, wherein at least one first polysiloxane vinyl crosslinker has a weight average molecular weight of about 8,000 daltons or more.

[0173] 4. A method in which, in Embodiment 2 or Embodiment 3, at least one first polysiloxane vinyl crosslinker has a weight average molecular weight of about 10,000 daltons or more.

[0174] 5. A method in which, in Embodiment 2 or Embodiment 3, at least one first polysiloxane vinyl crosslinking agent is present in an amount of about 45 weight% or more in the first polymerizable composition.

[0175] 6. A method in which, in Embodiment 2 or Embodiment 3, at least one first polysiloxane vinyl crosslinking agent is present in an amount of about 50 weight% or more in the first polymerizable composition.

[0176] 7. A method in which, in Embodiment 2 or Embodiment 3, at least one first polysiloxane vinyl crosslinking agent is present in an amount of about 55 weight% or more in the first polymerizable composition.

[0177] 8. A method in any one of embodiments 3 to 7, wherein the volume of the droplet is about 4.5 μL or less.

[0178] 9. A method in any one of embodiments 3 to 7, wherein the volume of the droplet is about 4.0 μL or less.

[0179] 10. A method in any one of embodiments 3 to 7, wherein the volume of the droplet is about 3.5 μL or less.

[0180] 11. In Embodiment 1, the curing step of (6) is performed thermally, and the at least one first and second free radical initiator comprises a thermal free radical initiator.

[0181] 12. In Embodiment 11, the curing step of (6) is performed with a chemical line, and the at least one first and second free radical initiator comprises a free radical photoinitiator.

[0182] 13. A method in any one of embodiments 1 to 12, wherein the at least one first and second polymerizable material independently comprises at least one component selected from the group consisting of (a) at least one silicon-containing vinyl monomer, (b) at least one second polysiloxane vinyl crosslinking agent, at least one non-silicon vinyl crosslinking agent, or a combination thereof, (c) at least one hydrophilic vinyl monomer, and optionally (d) a non-silicon hydrophobic vinyl monomer, a UV-absorbing vinyl monomer, and a combination thereof.

[0183] 14. A method according to Embodiment 13, wherein the at least one hydrophilic vinyl monomer comprises at least one hydrophilic (meth)acrylamido monomer.

[0184] 15. Method according to Embodiment 14, wherein at least one hydrophilic (meth)acrylamido monomer has 3 to 8 carbon atoms.

[0185] 16. In Embodiment 14, the at least one hydrophilic (meth)acrylamido monomer is (meth)acrylamide, N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-ethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-3-methoxypropyl (meth)acrylamide, N-2-hydroxyethyl (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N-4-hydroxybutyl (meth)acrylamide, N,N-bis(2-hydroxyethyl) (meth)acrylamide, N -Tris(hydroxymethyl)methyl(meth)acrylamide, 2-(meth)acrylamido-glycolic acid, 3-(meth)acrylamidopropionic acid, 4-(meth)acrylamido-butanoic acid, 3-(meth)acrylamido-2-methylbutanoic acid, 3-(meth)acrylamido-3-methylbutanoic acid, 2-(meth)acrylamido-2-methyl-3,3-dimethylbutanoic acid, 5-(meth)acrylamidopentanoic acid, 3-(meth)acrylamidohexanoic acid, 4-(meth)acrylamido-3,3-dimethylhexanoic acid, (3-(meth)acrylamidophenyl)boronic acid, 3-((3-methacrylamidopropyl)dimethylammonio)-propane-1-sulfonate; A method selected from the group consisting of 3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate, poly(ethylene glycol)ethyl (meth)acrylamide having a number average molecular weight of up to 700, methoxy-poly(ethylene glycol)ethyl (meth)acrylamide having a number average molecular weight of up to 700, and combinations thereof.

[0186] 17. A method in any one of embodiments 14 to 16, wherein the at least one hydrophilic (meth)acrylamido monomer comprises N,N-dimethyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-2-hydroxyethyl (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, (meth)acrylamide, or a combination thereof.

[0187] 18. A method in any one of embodiments 14 to 16, wherein the at least one hydrophilic (meth)acrylamido monomer comprises N,N-dimethyl (meth)acrylamide, N-2-hydroxyethyl (meth)acrylamide, or a combination thereof.

[0188] 19. A method in any one of embodiments 13 to 18, wherein the at least one hydrophilic vinyl monomer comprises at least one hydrophilic (meth)acryloxy monomer.

[0189] 20. In Embodiment 19, the at least one hydrophilic (meth)acryloxy monomer is 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycerol methacrylate (GMA), di(ethylene glycol) (meth)acrylate, tri(ethylene glycol) (meth)acrylate, tetra(ethylene glycol) (meth)acrylate, poly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, (meth)acrylic acid, ethylacrylic acid, propylacrylic acid, butylacrylic acid, trimethylammonium 2-hydroxypropyl (meth)acrylate hydrochloride, dimethylaminoethyl (meth)acrylate, ethylene glycol methyl ether (meth)acrylate, di(ethylene glycol) methyl ether A method selected from the group consisting of (meth)acrylate, tri(ethylene glycol) methyl ether (meth)acrylate, tetra(ethylene glycol) methyl ether (meth)acrylate, C1-C4-alkoxy poly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, and combinations thereof.

[0190] 21. In any one of embodiments 13 to 20, the at least one hydrophilic vinyl monomer is N-vinylpyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-6-methyl-2-pyrrolidone, N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, N-vinyl-3,3,5-trimethyl-2-pyrrolidone, N-vinylpiperidone ( life , N-vinyl-2-piperidone), N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone, N-vinyl-5-methyl-2-piperidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vinyl-4,4-dimethyl-2-piperidone, N-vinyl caprolactam( lifeA method comprising at least one hydrophilic N-vinylamide monomer selected from the group consisting of N-vinyl-2-caprolactam), N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-caprolactam, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5-dimethyl-2-caprolactam, N-vinyl-4,6-dimethyl-2-caprolactam, N-vinyl-3,5,7-trimethyl-2-caprolactam, N-vinyl-N-methylacetamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, and mixtures thereof.

[0191] 22. A method in any one of embodiments 13 to 20, wherein the at least one hydrophilic vinyl monomer comprises N-vinylpyrrolidone and / or N-vinyl-N-methylacetamide.

[0192] 23. In any one of embodiments 13 to 22, the at least one hydrophilic vinyl monomer is (a) 1-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, (b) at least one methylene-containing pyrrolidone monomer selected from the group consisting of 1-tert-butyl-3-methylene-2-pyrrolidone and combinations thereof; (b) at least one vinyl ether monomer selected from the group consisting of ethylene glycol monovinyl ether, di(ethylene glycol) monovinyl ether, tri(ethylene glycol) monovinyl ether, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, ethylene glycol methyl vinyl ether, di(ethylene glycol) methyl vinyl ether, tri(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether, and combinations thereof; (c) at least one allyl ether monomer selected from the group consisting of ethylene glycol monoallyl ether, di(ethylene glycol) monoallyl ether, tri(ethylene glycol) monoallyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, ethylene glycol methylallyl ether, di(ethylene glycol) methylallyl ether, tri(ethylene glycol) methylallyl ether, tetra(ethylene glycol) methylallyl ether, poly(ethylene glycol) methylallyl ether, and combinations thereof;(d) (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acryloylamino]-ethyl-2'-(trimethylammonio)-ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)-ethyl phosphate, 5-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 6-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)-ethyl phosphate, 2-((meth)acryloyloxy)-ethyl-2'-(triethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tripropylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tributylammonio)ethyl phosphate, 2-((meth)acryloyloxy)propyl-2'-(trimethylammonio)-ethyl phosphate, 2-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)-pentyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, At least one phosphorylcholine-containing vinyl monomer selected from the group consisting of 2-(vinyloxy)ethyl-2'-(trimethylammonio)-ethyl phosphate, 2-(allyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonyl)ethyl-2'-(trimethylammonio)-ethyl phosphate, 2-(vinylcarbonylamino)ethyl-2'-(trimethylammonio)-ethyl phosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(butenoyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, and combinations thereof; (e) allyl alcohol; (f) N-2-hydroxyethyl vinyl carbamate; (g) N-vinyloxycarbonyl-β-alanine (VINAL); (h) N-vinyloxycarbonyl-α-alanine;or (i) a method comprising a combination of these.;

[0193] 24. A method in any one of embodiments 13 to 23, wherein the at least one silicon-containing vinyl monomer comprises at least one silicon-containing (meth)acrylamido monomer containing a tris(trialkylsiloxy)silyl group.

[0194] 25. In Embodiment 24, the at least one silicon-containing (meth)acrylamido monomer containing a tris(trialkylsiloxy)silyl group is N-[tris(trimethylsiloxy)silylpropyl] (meth)acrylamide, N-[tris(dimethylethylsiloxy)-silylpropyl] (meth)acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl] (meth)acrylamide, N-[tris(dimethylphenylsiloxy)silylpropyl] (meth)acrylamide, N-(2-hydroxy-3-(3-(tris(trimethyl)-silyloxy)silyl)propyloxy)propyl)-2-methyl (meth)acrylamide, N-(2-hydroxy-3-(3-(tris(trimethyl-silyloxy)silyl)propyloxy)propyl) (meth)acrylamide, A method selected from the group consisting of N,N-bis[2-hydroxy-3-(3-(tris(trimethyl-silyloxy)silyl)propyloxy)propyl]-2-methyl (meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl](meth)acrylamide, and combinations thereof.

[0195] 26. A method in any one of embodiments 13 to 25, wherein the at least one silicon-containing vinyl monomer comprises at least one silicon-containing (meth)acrylamido monomer containing a bis(trialkylsilyloxy)-alkylsilyl group.

[0196] 27. In Embodiment 26, the at least one silicon-containing (meth)acrylamido monomer containing a bis(trialkylsilyloxy)alkylsilyl group is N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methyl (meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)-propyl) (meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]-2-methyl (meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)-propyl] (meth)acrylamide, Selected from the group consisting of N-[2-hydroxy-3-(3-(t-butyl-dimethylsilyl)propyloxy)propyl]-2-methylacrylamide, a siloxane-containing (meth)acrylamido monomer of one of the following chemical formulas Ia to Ih, and combinations thereof,

[0197] [Chemical Formula Ia]

[0198] ;

[0199] [Chemical Formula Ib]

[0200] ;

[0201] [Chemical Formula Ic]

[0202] ;

[0203] [Chemical Formula Id]

[0204] ;

[0205] [Chemical Formula Ie]

[0206] ;

[0207] [Chemical Formula If]

[0208] ;

[0209] [Chemical Formula Ig]

[0210] ;

[0211] [Chemical Formula Ih]

[0212] ,

[0213] In the above equation, R 13 -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, , , , , , , , , , or is a divalent alkylene radical, and R 14 is a divalent alkylene radical of -CH2CH2- or -CH2CH2CH2-, and R 15 Is or is a divalent alkylene radical, and R" and R 11 A method in which the groups are independently C1-C4 alkyls and f1 is an integer from 3 to 5.

[0214] 28. In any one of embodiments 13 to 27, the at least one silicon-containing vinyl monomer comprises at least one mono-(meth)acrylamido-terminated oligo- or polysiloxane of the following formula IIa, and

[0215] [Chemical Formula IIa]

[0216]

[0217] In the above formula, R' is hydrogen or methyl, R" is independently a C1-C6 alkyl, g1 and g2 are independently integers of 0 or 1, h1 is an integer from 2 to 25, and R9 and R 10 C1-C are independently substituted or non-substituted. 10 The alkylene divalent radical is, and Y1 is , , or It is a connector of, and R 12 and R 12' is independently C1-C6 alkyl, method.

[0218] 29. A method according to Embodiment 28, wherein in Formula IIa, h1 is an integer from 3 to 20 (more preferably from 3 to 15).

[0219] 30. In Embodiment 28 or Embodiment 29, in Formula IIa, R 12 and R 12 ' is independently methyl, method.

[0220] 31. In any one of embodiments 28 to 30, at least one mono-(meth)acrylamido-terminated oligo- or polysiloxane is α-(meth)acryloyl-amidopropyloxypropyl-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-N-methyl-(meth)acryloylamidopropyloxypropyl-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxy-propyl]-terminated ω-C1-C4-alkyl polydimethylsiloxane, α-[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxy-propyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylamido-isopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxy-propyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloylamido-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl polydimethylsiloxane, α-[3-[N-methyl-(meth)acryloylamido]-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, N-methyl-N'-(propyl-tetra(dimethylsiloxy)dimethylbutylsilane) (meth)acrylamide, A method selected from the group consisting of N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)dimethyl-butylsilane) (meth)acrylamide, (meth)acryloylamido-propyltetra(dimethylsiloxy)-dimethylbutylsilane, and combinations thereof.

[0221] 32. A method in any one of embodiments 13 to 31, wherein the at least one first polysiloxane vinyl crosslinking agent and the at least one second polysiloxane vinyl crosslinking agent are independently selected from the group consisting of α,ω-(meth)acryloxy-terminated polydimethylsiloxane; α,ω-(meth)acrylamido-terminated polydimethylsiloxane; α,ω-vinyl carbonate-terminated polydimethylsiloxane; α,ω-vinyl carbamate-terminated polydimethylsiloxane; bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane; reaction product of glycidyl methacrylate and diamino-functionalized polydimethylsiloxane; reaction product of azlactone-containing vinyl monomer and dihydroxy-functionalized polydimethylsiloxane; and combinations thereof.

[0222] 33. In any one of embodiments 13 to 31, the at least one first polysiloxane vinyl crosslinking agent and the at least one second polysiloxane vinyl crosslinking agent independently comprise at least one polysiloxane vinyl crosslinking agent of the following formula H, and

[0223] [Chemical Formula H]

[0224]

[0225] In the above formula:

[0226] d1 is an integer from 30 to 500 and d2 is an integer from 1 to 75, provided that d2 / d1 is about 0.035 to about 0.15 (preferably about 0.040 to about 0.12, more preferably about 0.045 to about 0.10);

[0227] X h1 is O or NR hN is R hN Silver, hydrogen, or C1-C 10 -alkyl and;

[0228] R h0 It is hydrogen or methyl;

[0229] R h1 and R h2 are independently substituted or non-substituted C1-C 10 alkylene divalent radical or -R h4 -OR h5 - is a divalent radical and R h4 and R h5 are independently substituted or non-substituted C1-C 10 It is an alkylene divalent radical;

[0230] R h3 is a monovalent radical of any one of the following chemical formulas Ha to He;

[0231] [Chemical Formula Ha]

[0232]

[0233] [Chemical Formula Hb]

[0234]

[0235] [Chemical Formula Hc]

[0236]

[0237] [Chemical Formula Hd]

[0238]

[0239] [Chemical formula He]

[0240]

[0241] k1 is 0 or 1; m1 is an integer from 2 to 4; m2 is an integer from 1 to 5; m3 is an integer from 3 to 6; m4 is an integer from 2 to 5;

[0242] R h6 It is hydrogen or methyl;

[0243] R h7 It is a C2-C6 hydrocarbon radical having an (m2+1) valence;

[0244] R h8 It is a C2-C6 hydrocarbon radical having an (m4+1) valence;

[0245] Rh9 is ethyl or hydroxymethyl;

[0246] R h10 is methyl or hydromethyl;

[0247] R h11 is hydroxyl or methoxy;

[0248] X h1 Silver -S- sulfur connector or -NR h12 - is the tertiary amino linker of and R h12 is a C1-C1 alkyl, hydroxyethyl, hydroxypropyl, or 2,3-dihydroxypropyl;

[0249] X h2 Is or It is a connector of and R h13 Silver, hydrogen, or C1-C 10 Alkyl, method.

[0250] 34. In any one of embodiments 13 to 31, the at least one first polysiloxane vinyl crosslinker and the at least one second polysiloxane vinyl crosslinker independently comprise (i) at least one polysiloxane vinyl crosslinker comprising one single polydiorganosiloxane segment and two terminal ethylene-based unsaturated groups (these are selected from the group consisting of (meth)acryloyloxy groups, (meth)acryloylamino groups, vinyl carbonate groups, and vinyl carbamate groups); and / or (ii) at least one chain-extended polysiloxane vinyl crosslinker comprising at least two polydiorganosiloxane segments and a covalent linker between each pair of polydiorganosiloxane segments and two terminal ethylene-based unsaturated groups (which are selected from the group consisting of (meth)acryloyloxy groups, (meth)acryloylamino groups, vinyl carbonate groups, and vinyl carbamate groups).

[0251] 35. In any one of embodiments 13 to 31, the at least one first polysiloxane vinyl crosslinker and the at least one second polysiloxane vinyl crosslinker are independently of each other (i) α,ω-bis[3-(meth)acrylamidopropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy-isopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamido-isopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutylamino-2-hydroxypropyloxy-propyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acrylamidoethylamino-2-hydroxypropyloxy-propyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamido-propylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamido-propylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,Comprising at least one polysiloxane vinyl crosslinker selected from the group consisting of ω-bis[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxyethylamino-carbonyloxyethoxy-propyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxyethylamino-carbonyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, and combinations thereof, method.,

[0252] 36. In any one of embodiments 13 to 31, the at least one first polysiloxane vinyl crosslinking agent and the at least one second polysiloxane vinyl crosslinking agent are independently of each other. It comprises at least one polysiloxane vinyl crosslinker having a polymer chain segment (i.e., a divalent radical), wherein SN is an integer of 3 or more and each R S1 and R S2 C1-C are independently of each other 10 Alkyl; Phenyl; C1-C4-alkyl-substituted phenyl; C1-C4-alkoxy-substituted phenyl; Phenyl-C1-C6-alkyl; C1-C 10 Fluoroalkyl; C1-C 10 Fluoroether; aryl; aryl C1-C 18 Alkyl; -alk-(OC2H4) γ1 -OR o (Here, alk is a C1-C6 alkylene diradal, and R o is H or C1-C4 alkyl and γ1 is an integer from 1 to 10); hydroxyl group (-OH), carboxyl group (-COOH), -NR N1 -'s amino linker, -CONR N1 -amide linker of, -CONR N1R N1 amide of, -OCONH- urethane linker, and C1-C4 alkoxy group, or linear hydrophilic polymer chain (where, R N1 and R N1 ' are independently hydrogen or C1-C 15 C2-C having at least one functional group selected from the group consisting of alkyls 40 A method selected from a group of organic radicals.

[0253] 37. In any one of embodiments 13 to 31, the at least one first polysiloxane vinyl crosslinking agent and the at least one second polysiloxane vinyl crosslinking agent independently comprise at least one polysiloxane vinyl crosslinking agent of the following formula 1 or 2, and

[0254] [Chemical Formula 1]

[0255]

[0256] [Chemical Formula 2]

[0257]

[0258] In the above formula:

[0259] R o is H or methyl;

[0260] υ1 is an integer from 30 to 500; υ2 and υ3 are independently integers from 5 to 100; ω2 and ω3 are independently integers from 1 to 15;

[0261] a1 and g1 are independently 0 or 1;

[0262] L1 is a C2-C8 alkylene divalent radical or , , , , , , or The divalent radical of;

[0263] L1' is a C2-C8 alkylene divalent radical having 0 or 1 hydroxyl group;

[0264] L1" is a C3-C8 alkylene divalent radical having 0 or 1 hydroxyl group;

[0265] L2 is , , , , or The divalent radical of;

[0266] L3 is The divalent radical of, and PE is or The divalent radical of;

[0267] L3' is a C3-C8 alkylene divalent radical;

[0268] R2 is C4-C 14 It is a divalent hydrocarbon radical;

[0269] R3 is a C2-C6 alkylene divalent radical;

[0270] X o , X1', and X o1 are independently O or NR1 and;

[0271] X1 is O, NR1, NHCOO, OCONH, CONR1, or NR1CO;

[0272] Z0 is directly bonded or C1-C 12 Method of an alkylene divalent radical.

[0273] 38. In any one of embodiments 13 to 37, the at least one silicon-containing vinyl monomer comprises at least one silicon-containing vinyl monomer of the following formula M1 or M2, and

[0274] [Chemical Formula M1]

[0275]

[0276] [Chemical Formula M2]

[0277]

[0278] In the above formula: a M1 is 0 or 1 and; R M0 is H or methyl; X M0 is O or NR M1 Igo; L M1 C2-C8 alkylene divalent radical or , , , , , , or The divalent radical of; L M1 ' is a C2-C8 alkylene divalent radical having 0 or 1 hydroxyl group; L M1 is a C3-C8 alkylene divalent radical having 0 or 1 hydroxyl group; X M1 은 O, NR M1 , NHCOO, OCONH, CONR M1 , or NR M1 CO and; R M1 is H, or a C1-C4 alkyl having 0 or 2 hydroxyl groups; R t1 and R t2 are independently C1-C6 alkyls; X M1 A method in which ' is O or NR1; v1 is an integer from 1 to 30; v2 is an integer from 0 to 30; n1 is an integer from 3 to 40; and r1 is an integer from 2 or 3.

[0279] 39. In Embodiment 38, the at least one silicon-containing vinyl monomer is tris(trimethylsilyloxy)silylpropyl(meth)acrylate, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)methylsilane, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)butylsilane, 3-(meth)acryloxy-2-(2-hydroxyethoxy)propyloxy)propylbis(trimethylsiloxy)methylsilane, 3-(meth)acryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane, N-2-(meth)acryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silyl carbamate, 3-(trimethylsilyl)propylvinyl carbonate, A method comprising 3-(vinyloxycarbonylthio)propyltris(trimethylsiloxy)silane, 3-[tris(trimethylsiloxy)silyl]-propylvinyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate, 3-[tris(trimethylsiloxy)silyl]-propyl vinyl carbonate, or a combination thereof.

[0280] 40. In any one of embodiments 13 to 37, the at least one silicon-containing vinyl monomer is α-(meth)acryloxypropyl-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-(meth)acryloxy-2-hydroxypropyloxypropyl-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-(2-hydroxyl-methacryloxypropyloxypropyl)-ω-C1-C4-alkyl-decamethylpentasiloxane, α-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloxy-propyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloxyisopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloxy-butylamino-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[(meth)acryloxy-(polyethyleneoxy)-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-[(meth)acryloxy-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane,A method comprising at least one silicone-containing vinyl monomer selected from the group consisting of α-vinyl carbonate-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-vinyl carbamate-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, or mixtures thereof.

[0281] 41. A method in any one of embodiments 13 to 40, wherein the sum of the amounts of components (a), (b), and (c) in the monomer mixture is at least about 60% by weight relative to the total weight of all polymerizable materials present in the monomer mixture.

[0282] 42. A method in any one of embodiments 13 to 40, wherein the sum of the amounts of components (a), (b), and (c) in the monomer mixture is at least about 65% by weight relative to the total weight of all polymerizable materials present in the monomer mixture.

[0283] 43. A method in any one of embodiments 13 to 40, wherein the sum of the amounts of components (a), (b), and (c) in the monomer mixture is at least about 70 weight% relative to the total weight of all polymerizable materials present in the monomer mixture.

[0284] 44. A method in any one of embodiments 13 to 40, wherein the sum of the amounts of components (a), (b), and (c) in the monomer mixture is at least about 75% by weight relative to the total weight of all polymerizable materials present in the monomer mixture.

[0285] 45. A method in any one of embodiments 1 to 44, wherein the at least one first and second polymerizable material independently comprises at least one non-silicon vinyl crosslinking agent.

[0286] 46. ​​In any one of Embodiments 1 to 44, the at least one first and second polymerizable material is independently ethylene glycol di-(meth)acrylate, diethylene glycol di-(meth)acrylate, triethylene glycol di-(meth)acrylate, tetraethylene glycol di-(meth)acrylate, glycerol di-(meth)acrylate, 1,3-propanediol di-(meth)acrylate, 1,3-butanediol di-(meth)acrylate, 1,4-butanediol di-(meth)acrylate, glycerol 1,3-diglycerolate di-(meth)acrylate, ethylenebis[oxy(2-hydroxypropane-1,3-diyl)] di-(meth)acrylate, bis[2-(meth)acryloxyethyl] phosphate, trimethylolpropane di-(meth)acrylate, and 3,4-Bis[(meth)acryloyl]tetrahydrofuran, diacrylamide (i.e., N-(1-oxo-2-propenyl)-2-propenamide), dimethacrylamide (i.e., N-(1-oxo-2-methyl-2-propenyl)-2-methyl-2-propenamide), N,N-di(meth)acryloyl-N-methylamine, N,N-di(meth)acryloyl-N-ethylamine, N,N'-methylene bis(meth)acrylamide, N,N'-ethylene bis(meth)acrylamide, N,N'-dihydroxyethylene bis(meth)acrylamide, N,N'-propylene bis(meth)acrylamide, N,N'-2-hydroxypropylene bis(meth)acrylamide, N,N'-2,3-dihydroxybutylene bis(meth)acrylamide, 1,3-Bis(meth)acrylamide-propane-2-yl dihydrogen phosphate (i.e., N,N'-2-phosphonyloyl oxypropylene bis(meth)acrylamide), piperazine diacrylamide (or 1,4-Bis(meth)acryloyl piperazine), tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, trialyl isocyanurate, trialyl cyanurate, trimethylpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate,A method comprising at least one non-silicon vinyl crosslinking agent selected from the group consisting of combinations thereof.

[0287] 47. A method in any one of embodiments 1 to 44, wherein the at least one first and second polymerizable material independently comprises at least one non-silicon vinyl crosslinking agent selected from the group consisting of tetra(ethylene glycol) di-(meth)acrylate, tri(ethylene glycol) di-(meth)acrylate, ethylene glycol di-(meth)acrylate, di(ethylene glycol) di-(meth)acrylate, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, trialyl isocyanurate, trialyl cyanurate, or a combination thereof.

[0288] 48. A method in any one of embodiments 1 to 47, wherein the at least one first and second polymerizable material independently comprises at least one non-silicon hydrophobic vinyl monomer.

[0289] 49. In any one of Embodiments 1 to 47, the at least one first and second polymerizable material are independently at least one C1-C8 alkyl (meth)acrylate, at least one C5-C 16 A method comprising cycloalkyl (meth)acrylate, at least one aryl methacrylate, (meth)acrylonitrile, at least one fluorine-containing acrylic monomer, at least one vinyl alkanoate, at least one vinyloxyalkane, at least one substituted or unsubstituted styrene, vinyl toluene, vinyl chloride, vinylidene chloride, 1-butene, or a combination thereof.

[0290] 50. In Embodiment 49, the at least one vinyl alkanoate is selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, and combinations thereof, the at least one vinyloxyalkane is selected from the group consisting of vinyl ethyl ether, propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, t-butyl vinyl ether, and combinations thereof, and the at least one fluorine-containing acrylic monomer is 2,2,2-trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoro-iso-propyl (meth)acrylate, hexafluorobutyl (meth)acrylate, heptafluorobutyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, pentafluorophenyl A method selected from the group consisting of (meth)acrylates, perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylates, and combinations thereof.

[0291] 51. A method in any one of embodiments 1 to 47, wherein the at least one first and second polymerizable material independently comprises methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, phenyl methacrylate, 4-tert-butylstyrene, 2-methylstyrene, styrene, 4-ethoxystyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, or a combination thereof.

[0292] 52. A method in any one of embodiments 1 to 47, wherein the at least one first and second polymerizable material independently comprises methyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, or a combination thereof.

[0293] 53. A method in any one of embodiments 1 to 47, wherein the at least one first and second polymerizable material independently comprises methyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, or a combination thereof.

[0294] 54. A method in any one of embodiments 1 to 53, wherein the at least one first and second polymerizable material independently comprises at least one UV-absorbing vinyl monomer.

[0295] 55. A method in any one of embodiments 1 to 53, wherein at least one first and second polymerizable material independently comprises 2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole (Norbloc).

[0296] 56. In any one of Embodiments 1 to 55, the at least one photochromic compound is naphtopyran, indeno-fused naphtopyran (i.e., indeno-naphtopyran), heterocyclic ring-fused naphtopyran, benzopyran, phenantropyran, quinopyran, quinolinopyran, fluoroantenopyran, anthracene-fused pyran, tetracene-fused pyran, spiro(benzindolin)naphtopyran, spiro(indolin)naphtopyran, spiro(indolin)benzopyran, spiro(indolin)quinopyran, spiro(indolin)pyran, naphthoxazine, spirobenzopyran, spirobenzothiopyran, naphthacenedione, benzoxazine, spirooxazine, naphthoxazine, spiro(benzindolin)naphthoxazine, spiro(indolin)naphthoxazine, Spiro(indoline)pyrido-benzoate, Spiro(indoline)benzoate, Spiro(benzindolin)benzoate, Spiro(benzindolin)pyridobenzoate, Spiro(indoline)fluolanthenox, Spiro(indoline)-quinox, Spiropiperidine-naphtopyran, Pyro(indoline)pyronobenzoate, Benzospiropyran, Naphtospiropyran, Spirobenzoate-pyrrolopyridine, Spironaftox-pyrrolopyridine, Spiro-oxazepine-benzoate, Spiro(indoline)benzophyrolox, Spiro(indoline)quinazolino-oxoate, Spiro(indoline)anthracenobenzoate, Benzofurobenzopyran, A method comprising benzothienobenzopyran, naphthofurobenzopyran, benzopyrano-fused naphthofyran, spiro(isoindoline)-naphtoxazine, spiro(isoindoline)benzoxazine, or a mixture thereof.

[0297] 57. A method in any one of embodiments 1 to 56, wherein at least one photochromic compound is polymerizable (i.e., containing an ethylene-based unsaturated group).

[0298] 58. In Embodiment 57, the at least one photochromic compound is a coupling reaction product of a reactive (meth)acrylamido or (meth)acryloxy monomer having a first reactive functional group, and the reactive photochromic compound has a second reactive functional group in the absence or presence of a coupling agent during the coupling reaction, and the first reactive functional group is -COCl, -COBr, -COOH, -NHR N2 , -NCO, -OH, -CHO, , , or Selected from the group consisting of, and the second reactive functional group is -COOH, -NHR N2 , , , , -NCO, -OH, -SH, -CHO, , , or Selected from the group consisting of, where R0 is hydrogen or methyl and R N2 is hydrogen, linear or branched C1-C 15 A method in which alkyl, cyclohexyl, cyclopentyl, substituted or unsubstituted phenyl, or substituted or unsubstituted phenyl-C1-C6 alkyl.

[0299] 59. In Embodiment 58, the reactive (meth)acrylamido or (meth)acryloxy monomer is a (meth)acryloyl halide (CH2=CH─COX or CH2=CCH3─COX, X=Cl or Br), N-hydroxysuccinimide ester of (meth)acrylic acid, glycidyl (meth)acrylate, isocyanato-C2-C6 alkyl (meth)acrylate, amino-C2-C6 alkyl (meth)acrylamide, C1-C6 alkylamino-C2-C6 alkyl (meth)acrylamide, (meth)acrylic acid, C2-C4 alkylacrylic acid (e.g., ethylacrylic acid, propylacrylic acid, butylacrylic acid), N-2-acrylamidoglycolic acid, 3-(acryloyloxy)propanoic acid, C2-C6 hydroxyalkyl (Met)acrylate, C2-C6 hydroxyalkyl (meth)acrylamide, azlactone-containing vinyl monomer (e.g., 2-vinyl-4,4-dimethyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one, 2-vinyl-4-methyl-4-ethyl-1,3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-butyl-1,3-oxazolin-5-one, 2-vinyl-4,4-dibutyl-1,3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-dodecyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-diphenyl-1,3-oxazolin-5-one, As 2-isopropen-4,4-pentamethylene-1,3-oxazolin-5-one, 2-isopropen-4,4-tetramethylene-1,3-oxazolin-5-one, 2-vinyl-4,4-diethyl-1,3-oxazolin-5-one, 2-vinyl-4-methyl-4-nonyl-1,3-oxazolin-5-one, 2-isopropen-4-methyl-4-phenyl-1,3-oxazolin-5-one, 2-isopropen-4-methyl-4-benzyl-1,3-oxazolin-5-one, 2-vinyl-4,4-pentamethylene-1,3-oxazolin-5-one, and 2-vinyl-4,4-dimethyl-1,3-oxazolin-6-one, the preferred azlactone-containing vinyl monomer is 2-vinyl-4,4-dimethyl-1,3-oxazolin-5-one (VDMO) and 2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one (IPDMO), aziridinyl C1-C 12A method selected from the group consisting of alkyl (meth)acrylates (e.g., 2-(1-aziridinyl)ethyl (meth)acrylate, 3-(1-aziridinyl)propyl (meth)acrylate, 4-(1-aziridinyl)butyl (meth)acrylate, 6-(1-aziridinyl)hexyl (meth)acrylate, or 8-(1-aziridinyl)octyl (meth)acrylate), acrolein, methacrolein, crotonaldehyde, and combinations thereof.

[0300] 60. In Embodiment 58 or Embodiment 59, the reactive photochromic compound is 3,3-bis(4-methoxyphenyl)-6,11-dimethyl-13-hydroxyethoxy-13-phenyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-bis(4-methoxyphenyl)-6,11-dimethyl-13-(2-hydroxycarbonylethyl)carboxyethoxy-13-phenyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-bis(4-methoxyphenyl)-6,11-dimethyl-13-hydroxy-13-phenyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-Bis(4-methoxyphenyl)-6,11-dimethyl-13-(2-hydroxycarbonylethyl)carboxy-13-phenyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-Bis(4-methoxyphenyl)-6,11-dimethyl-13-hydroxy-13-propyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-Bis(4-methoxyphenyl)-6,11-dimethyl-13-(2-hydroxycarbonylethyl)carboxy-13-propyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-10,11-dimethoxy-13-hydroxy-13-ethyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-10,11-dimethoxy-13-(2-hydroxycarbonylethyl)carboxy-13-ethyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-bis(4-methoxyphenyl)-7-methoxy-11-phenyl-13-hydroxymethyl-13-methyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-Bis(4-methoxyphenyl)-7-methoxy-11-phenyl-13-(2-hydroxycarbonylethyl)carboxymethyl-13-methyl-3H,13H-indeno[2',3':3,4]-naphtho[1,2-b]pyran; 3,3-Bis(4-methoxyphenyl)-7-methoxy-11-phenyl-13-hydroxy-13-methyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;3,3-Bis(4-methoxyphenyl)-7-methoxy-11-phenyl-13-(2-hydroxycarbonylethyl)carboxy-13-methyl-3H,13H-indeno-[2',3':3,4]naphtho[1,2-b]pyran; 3,3-Bis(4-methoxyphenyl)-11-phenyl-13-hydroxy-13-methyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-Bis(4-methoxyphenyl)-11-phenyl-13-(2-hydroxycarbonylethyl)carboxy-13-methyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-6,7,10,11-tetramethoxy-13-hydroxy-13-ethyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-bis(4-methoxyphenyl)-6,7,10,11-tetramethyl-13-(2-hydroxycarbonylethyl)carboxy-13-methyl-3H,13H-indeno[2',3':3,4]-naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-6,7-dimethoxy-13-hydroxy-13-ethyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-bis(4-methoxyphenyl)-11-(4-(4,5-diphenyl-1H-imidazole-2-yl)phenyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-6-methoxy-7-(3-hydroxymethylenepiperidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1.2-b]pyran; 3,3-di(4-methoxyphenyl)-6-methoxy-7-(3-(2-hydroxycarbonylethyl)-carboxymethylenepiperidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-6,7-dimethoxy-13-hydroxy-13-butyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-6,11,13-trimethyl-13-(2-(2-hydroxyethoxy)-ethoxy)-indeno[2,1-f]naphtho[1,2-b]pyran;3,3-di(4-methoxyphenyl)-6,11,13-trimethyl-13-(2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)ethoxy)-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-diphenyl-13-hydroxy-13-(2-oxo-2-ethoxyethyl)-1H-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-6,11-dimethyl-13-hydroxy-13-(2-oxo-2-ethoxyethyl)-1H-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-6,11-dimethyl-13-butyl-13-hydroxy-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-bis(4-hydroxyphenyl)-7-methoxy-11-phenyl-13,13-diethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-bis(4-hydroxyphenyl)-7-methoxy-11-phenyl-13,13-dipropyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-Bis(4-hydroxyphenyl)-7-methoxy-11-phenyl-13-carbomethoxy-13-methyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-diphenyl-6,7-dimethoxy-13-methyl-13-methyl-13-hydroxyethoxyethoxy-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-diphenyl-6,7,10,11-tetramethoxy-13-ethyl-13-methyl-13-hydroxyethoxyethoxy-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 6,7-Dimethoxy-2,2-Diphenyl-13-hydroxy-13-butyl-2H,13H-Indeno[1',2':4,3]Naphtho[1,2-b]pyran; 6,7-Dimethoxy-2,2-Diphenyl-13-hydroxy-13-methyl-2H,13H-Indeno[1',2':4,3]Naphtho[1,2-b]pyran; 6,7-Dimethoxy-2,2-Diphenyl-13-hydroxy-2H,13H-Indeno[1',2':4,3]Naphtho[1,2-b]pyran; 3-(4-allyloxyphenyl)-3-(4-morpholinophenyl)-7-methoxy-11-phenyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;3-(4-fluorophenyl)-3-(4-butoxyphenyl)-10-(piperazine-1-yl)-6-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3:4]naphtho[1,2-b]pyran; 3-(4-fluorophenyl)-3-(4-butoxyphenyl)-10-(4-hydroxybenzamido)-6-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3:4]naphtho[1,2-b]pyran; 3-(4-fluorophenyl)-3-(4-butoxyphenyl)-10-vinyl-6-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3:4]naphtho[1,2-b]pyran; 3-(4-fluorophenyl)-3-(4-butoxyphenyl)-10-(carboxylic acid)-6-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3:4]naphtho[1,2-b]pyran; 3-(4-fluorophenyl)-3-(4-methoxyphenyl)-6-methoxy-7-(4-hydroxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-(4-fluorophenyl)-3-(4-methoxyphenyl)-6-methoxy-7-(4-(2-hydroxycarbonylethyl)carboxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-(4-fluorophenyl)-3-(4-morpholinophenyl)-6-methoxy-7-(4-hydroxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1.2-b]pyran; 3-(4-fluorophenyl)-3-(4-morpholinophenyl)-6-methoxy-7-(4-(2-hydroxycarbonylethyl)carboxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-(4-hydroxyethoxyphenyl)-3-(4-methoxyphenyl)-11-(4-(N,N-dimethylamino)phenyl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(2,4-dimethoxyphenyl)-phenyl-6,11-dimethoxy-13-methyl-13-methyl-13-hydroxyethoxyethoxyethoxy-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;3-(4-methoxyphenyl)-3-(3-methyl-4-methoxyphenyl)-13-hydroxy-indeno[2,1-f]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6,7,10,11-tetramethoxy-13-hydroxy-13-ethyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6,7,10,11-tetramethoxy-13-hydroxy-13-butyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6,7-dimethoxy-13-hydroxy-13-ethyl-3H,13H-deno[2,1-f]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6,7-dimethoxy-13-hydroxy-13-methyl-3H,13H-deno[2,1-f]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-13-oxo-3H,13H-deno[2,1-f]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-phenyl-6-methoxy-7-morpholino-13-methyl-13-methyl-13-hydroxyethoxyethoxyethoxy-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-phenyl-6,11-dimethoxy-13-methyl-13-methyl-13-hydroxyethoxy-ethoxy-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 2-(4-methoxyphenyl)-2-(4-morpholinophenyl)-5-hydroxy-6-carboethoxy-2H-naphtho[1,2-b]pyran; 3-(4-morpholinophenyl)-3-phenyl-6,7-dimethoxy-13-hydroxy-13-ethyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3-(4-morpholinophenyl)-3-phenyl-6,7-dimethoxy-13-hydroxy-13-butyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3-(4-morpholinophenyl)-3-phenyl-6,7-dimethoxy-13-oxo-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran;3-phenyl-3-(4-hydroxyethoxyphenyl)-6-methoxy-7-morpholino-13,13-dimethyl-3H,13H-indeno-[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(2-hydroxycarbonylethyl)carboxyethoxy-phenyl)-6-methoxy-7-morpholino-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(2-hydroxyethoxy)phenyl)-6-methoxy-7-piperidino-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(2-(2-hydroxycarbonylethyl)-carboxyethoxy)phenyl)-6-methoxy-7-piperidino-13,13-dimethyl-3H,13H-indene[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-hydroxyphenyl)-6,7-dimethoxy-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-hydroxyethoxy)phenyl)-6,7-dimethoxy-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(2-hydroxycarbonylethyl)carboxyethoxy)phenyl)-6,7-dimethoxy-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(2-hydroxycarbonylethyl)carboxy-phenyl)-6,7-dimethoxy-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(4-(2-hydroxyethyl)piperazine-1-yl)phenyl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(4-(2-(2-hydroxycarbonylethyl)-carboxyethyl)piperazine-1-yl)phenyl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho-[1,2-b]pyran; 3-phenyl-3-(4-methoxyphenyl)-6-methoxy-7-piperazinyl-13,13-dimethyl-3H,13H-indene[2',3':3,4]naphtho[1,2-b]pyran;3-phenyl-3-(4-methoxyphenyl)-6-methoxy-7-(3-hydroxymethylenepiperidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3":3.4]naphtho[1.2-b]pyran; 3-phenyl-3-(4-methoxyphenyl)-6-methoxy-7-(3-(2-hydroxycarbonylethyl)carboxymethylenepiperidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3":3.4]naphtho[1.2-b]pyran; 3-phenyl-3-(4-methoxyphenyl)-6-methoxy-7-(4-hydroxypifenidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho-[1,2-b]pyran; 3-phenyl-3-(4-methoxyphenyl)-6-methoxy-7-(4-(2-hydroxycarbonylethyl)-carboxypifenidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(4-methoxyphenyl-piperazine-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-hydroxy-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(4-methoxyphenyl-piperazine-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(2-hydroxy-2-methyl-3-butin-4-yl)-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-morpholinophenyl)-6-methoxy-7-(3-hydroxymethylene-piperidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho-[1,2-b]pyran; 3-phenyl-3-(4-morpholinophenyl)-6-methoxy-7-(3-(2-hydroxycarbonyl-ethyl)carboxymethylene-piperidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3.4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-morpholinophenyl)-6-methoxy-7-(3-(2-hydroxycarbonylethyl)carboxymethylene-piperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-morpholinophenyl)-6-methoxy-7-(4-hydroxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1.2-b]pyran;3-phenyl-3-(4-morpholinophenyl)-6-methoxy-7-(4-(2-hydroxycarbonylethyl)-carboxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-morpholinophenyl)-6-methoxy-7-piperazinyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-morpholinophenyl)-6,11-dimethyl-13-hydroxy-13-(1-oxo-methoxyprop-2-yl)-1H-indeno[2,1-f]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(4-phenylpiperazino)-phenyl)-6-methoxy-7-(4-hydroxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1.2-b]pyran; 3-phenyl-3-(4-(4-phenylpiperazino)phenyl)-6-methoxy-7-(4-(2-hydroxycarbonylethyl)carboxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1.2-b]pyran; 3-phenyl-3-(4-piperazinylphenyl)-6,11-dimethoxy-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho-[1,2-b]pyran; 3-phenyl-3-(4-piperazinylphenyl)-6-methoxy-7-piperidinyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(3-methylpiperazine-1-yl)phenyl)-6-methoxy-7-(decahydroisoquinoline-2-yl)-11-tert-butyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-16-(ethoxycanobyl)methyl-16-hydroxy-3,16-dihydrobenzofuro-[2',3':7,8]indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-methoxyphenyl)-16-(ethoxycanobyl)-methyl-16-hydroxy-3,16-dihydrobenzofuro-[2",3":6',7']indeno-[3',2':4,3]naphtho[1,2-b]pyran;3-phenyl-3-(4-morpholinophenyl)-16-(ethoxycanobyl)-methyl-16-hydroxy-3,16-dihydrobenzofuro[2',3':6',7']deno[3',2':4,3]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-16-(ethoxycarbonyl)methyl-16-hydroxy-3,16-dihydrobenzofuro[2',3':7,8]deno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-16-hydroxy-16-ethyl-16H-benzofuro[2',3':7,8]indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-16-hydroxy-16H-benzofuro[2",3":6,7]indeno[3',2':4,3]naphtho-[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-16-hydroxy-16-ethyl-16H-benzofuro[2",3":6,7]-indeno[3',2':4,3]naphtho[1,2-b]pyran; A method comprising 3-(4-methoxyphenyl)-3-(2,3-dihydrobenzofuro-5-yl)-13-hydroxy-13-methyl-indeno[2,1-f]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(2,3-dihydrobenzofuro-5-yl)-6,11-difluoro-13-hydroxy-13-(1-oxo-methoxyprop-2-yl)-1H-indeno[2,1-f]naphtho[1,2-b]pyran, or a mixture thereof.;

[0301] 61. In Embodiment 58 or Embodiment 59, the reactive photochromic compound is 2,2-di(4-fluorophenyl)-5-hydroxycarbonyl-6-phenyl-9-methoxy-2H-naphtho[1,2-b]pyran; 2,2-bis(4-methylphenyl)-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-methoxycarbonyl-6-hydroxy-[2H]-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-methoxyethoxycarbonyl-6-methyl-8-vinyl-2H-naphtho[1,2-b]pyran; 2,2-Bis(4-methoxyphenyl)-5-methoxyethoxycarbonyl-6-methyl-8-hydroxycarbonyl-2H-naphtho[1,2-b]pyran; 2,2-Bis(4-methoxyphenyl)-5-methoxycarbonyl-6-(2-hydroxyethoxy)ethoxy-[2H]-naphtho[1,2-b]pyran; 2,2-Bis(4-methoxyphenyl)-5-methoxycarbonyl-6-phenyl-9-(2-hydroxyethoxy)-[2H]-naphtho[1,2-b]pyran; 2,2-Bis(4-methoxyphenyl)-5-methoxy-carbonyl-6-(4-(2-hydroxyethoxy)phenyl)-[2H]-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-diphenylmethylol-6-hydroxy-2H-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-diphenylmethylol-6-methoxy-2H-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-(2-hydroxyethoxylcarbonyl)-6-phenyl-[2H]-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-(2-(2-hydroxyethoxy)-ethoxycarbonyl)-6-phenyl-[2H]-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-(2-(2-(2-hydroxyethoxy)ethoxy)-ethoxycarbonyl)-6-phenyl-[2H]-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-(2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)-ethoxycarbonyl)-6-phenyl-[2H]-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-hydroxymethyl-6-methyl-9-methoxy-2H-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-hydroxymethyl-6-phenyl-2H-naphtho[1,2-b]pyran;2,2-bis(4-methoxyphenyl)-5-hydroxymethyl-6-methoxy-2H-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-methoxycarbonyl-6-(3-aminophenyl)-2H-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-2,5,7-trihydro-7-methylidine-5-oxo-furo-[3',4':3,4]naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-phenylthio-6-hydroxy-2H-naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-13-hydroxy-13-methyl-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-9-methoxycarbonyl-8-(2-hydroxyethoxy)ethoxy-[3H]-naphtho[1,2-b]pyran; 2,2-diphenyl-5-hydroxycarbonyl-9-methoxy-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-5-hydroxycarbonyl-8,9-dimethoxy-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-5-hydroxy-6-carboethoxy-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-5-hydroxy-6-morpholinocarbonyl-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-5-hydroxy-6-carboethoxy-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-5-hydroxy-6-carbomethoxy-9-methoxy-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-5-hydroxy-6-morpholinocarbonyl-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-5-methylol-6-(3-dimethylaminopropyl)-methylamino-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-2,5,7-trihydro-7-methylidene-5-oxofuro-[3',4':3,4]naphtho[1,2-b]pyran; 2,2-spiroadamantylene-5-phenylthio-6-hydroxy-2H-naphtho[1,2-b]pyran; 2,2-diphenyl)-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 2,2-spiro-admamtylene-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran, 3,3-diphenyl-8-hydroxy-9-carbopropoxy-3H-naphtho[2,1-b]pyran; 2,2,5-triphenyl-6-carboethoxy-2H-naphtho[1,2-b]pyran;2,2,6-triphenyl-5-(2-(2-(2-(2-hydroxyethoxy)ethoxy)-ethoxy)ethoxy)carbonyl-[2H]-naphtho[1,2-b]pyran; 2,2,6-triphenyl-5-(2-(2-(2-oxiran-2-ylmethoxy)ethoxy)ethoxy)-ethoxycarbonyl)-[2H]-naphtho[1,2-b]pyran; 2-(4-methoxyphenyl)-2-(4-morpholinophenyl)-5-hydroxy-6-carboethoxy-2H-naphtho[1,2-b]pyran; 2-(4-methoxyphenyl)-2-tert-butyl-5-methoxy-carbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 2-(4-methoxyphenyl)-2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 2-(4-(2-(2-hydroxyethoxy)ethoxy)-ethoxyphenyl)-2-phenyl-5-methoxycarbonyl-6-methyl-9-methoxy-[2H]-naphtho[1,2-b]pyran; 2-(4-(2-(2-hydroxyethoxy)ethoxy)phenyl)-2-phenyl-5-methoxycarbonyl-6-(2-(2-methylprop-2-enoxyloxy)ethoxy)-[2H]-naphtho[1,2-b]pyran; 3-(4-(2-(2-hydroxyethoxy)-ethoxy)ethoxyphenyl)-3-phenyl-9-methoxycarbonyl-8-methoxy-[3H]-naphtho[1,2-b]pyran; 2-(4-morpholinophenyl)-2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 2-(9-ethylcarbazole-2-yl)-2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 2-(9-phenylcarbazole-2-yl)-2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 2-(4-dimethylaminophenyl)-2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 3-(2-fluorophenyl)-3-(4-methoxyphenyl-8-hydroxy-9-carbopropoxy-3H-naphtho[2,1-b]pyran; 3-(2-fluorophenyl)-3-(4-methoxyphenyl-8-hydroxy-9-carbomethoxy-3H-naphtho[2,1-b]pyran; 3-(2,4-dimethoxyphenyl)-3-(4-methoxyphenyl-8-hydroxy-9-carbomethoxy-3H-naphtho[2,1-b]pyran;3-(2,4,6-trifluorophenyl)-3-(2,4,6-trimethoxy-1-naphthyl)-8-acetyl-9-carbonylloyl-3H-naphtho[2,1-b]pyran; 3-(4-methoxyphenyl)-3-(2-methyl-2,3-dihydrobenzofuro-5-yl)-6-methoxy-12-hydroxymethyl-11-phenyl-3H-phenantro[1,2-b]pyran; 5,5-bis(4-methoxyphenyl)-8-methylol-5H-fluoranteno[3,2-b]pyran; or a mixture thereof, a method.;

[0302] 62. In Embodiment 58 or Embodiment 59, the reactive photochromic compound is 1-hydroxyethyl-3,3-dimethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1-hydroxypropyl-3,3-dimethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1-aminoethyl-3,3-dimethyl-5-chlorospiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1-hydroxyethyl-3,3-dimethyl-8'-methoxyspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1-(p-vinylphenyl)-3,3-dimethyl-5,6-dichlorospiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1,3,3-trimethyl-9'-hydroxyspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1,3,3-trimethyl-5'-hydroxymethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1,3,3-trimethyl-9'-aminospiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1,3,3-trimethyl-5-chloro-8'-hydroxyspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1-benzyl-3,3-dimethyl-9'-vinylbenzoyoxyspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1-benzyl-3,3-dimethyl-5'-hydroxymethylpiperidinospironaphthooxazine; 1,3,3-trimethyl-9'-hydroxyspiro[indolin-2,3'-[3H]-pyrido-[2,1-b][1,4]benzoxazine]; 5-hydroxy-6'-cyano-1,3,3-trimethyl-spiro-[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 5-hydroxy-6'-phenylsulfonyl-1,3,3-trimethyl-spiro-[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 5'formyl-1,3,3-trimethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine; 1,3-dihydro-6'-piperazino-1,3,3-trimethylspiro[2H indole-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine;1,3-Dihydro-6'-(4-hydroxyethyl)piperazino-1,3,3-trimethylspiro[2H indole-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine; 1,3-Dihydro-9'-hydroxy-1,3,3-trimethylspiro[2H indole-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine; 1,3,3,4,5-pentamethyl-9'-methoxycarbonyl-8'-hydroxy-spiro[indolin-2,3'-[3H]naphtho[2,1-b][1,4]oxazine; 1,3,3,5,6-pentamethyl-9'-methoxycarbonyl-8'-hydroxy-spiro[indolin-2,3'-[3H]napt[2,1-b][1,4]oxazine; 1-propyl-3,3,4,5-tetramethyl-9'-methoxycarbonyl-8'-hydroxy-spiro[indolin-2,3'-[3H]napt[2,1-b][1,4]oxazine; 1-propyl-3,3,5,6-tetramethyl-9'-methoxycarbonyl-8'-hydroxy-spiro[indolin-2,3'-[3H]napt[2,1-b][1,4]oxazine; 1-Methoxyethyl-3,3-Dimethyl-9'-Allyloxycarbonyl-8'-Chloroactoxy-spiro[Indolin-2,3'-[3H]Napt[2,1-b][1,4]Oxazine; 1-Allyl-3,3-Spirocyclohexyl-9'-Benzyloxycarbonyl-8'-Chloroactoxy-spiro[Indolin-2,3'-[3H]Napt[2,1-b][1,4]Oxazine; 5-Amino-1,3,3-Trimethyl-spiro[Indolin-2,3'-[3H]-Pyrido[3,4-f][1,4]-Benzoxazine; 6-Hydroxy-1',3',3',4',5'-Pentamethylspiro[2H-1,4-Benzoxazine-2,2'-Indolin]; 6-hydroxy-1',3',3',5',6'-pentamethylspiro[2H-1,4-benzoxazine-2,2'-indolin]; 5,7-dimethoxy-1'-hydroxy-carbonylethyl-3',3'-dimethylspiro[2H-1,4-benzoxazine-2,2'-indolin]; 7-methoxy-1'-hydroxy-ethyl-3',3'-dimethylspiro[2H-1,4-benzoxazine-2,2'-indolin]; 9'-hydroxy-1-methylspiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine]; 5-chloro-9'-hydroxy-1-methylspiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine];8'-hydroxy-1-methylspiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine]; 8'-hydroxy-5-methoxy-1-methylspiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine]; 8'-hydroxy-1,4,5-trimethylspiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine]; 9'-hydroxy-1-isopropylspiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine]; 9'-hydroxy-1-hexadecyl-spiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine]; 9'-hydroxy-1-octadecylspiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine]; 1,1"-(1,5-pentanediyl)bis[3,3-dimethyl]-9'-hydroxy-spiro[indolin-2,3'-[3H]-naphtho[2,1-b] [1,4]oxazine]; 1,1"-[1,4-phenylenebis(methylene)]bis[3,3-dimethyl]-5'-hydroxymethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b] [1,4]oxazine]; 1,1"-(1,4-butanediyl)bis[5,6-dichloro-3,3-dimethyl]-8'-hydroxyspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1,3,3-trimethyl-9'-hydroxypiperidinospyronafthoxazine; 3-carboxyethyl-1,1-dimethyl-9'-methoxyspiro[benz[e]-indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1-carboxyethyl-3,3-dimethyl-9'-methoxyspiro[benz[g]-indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1,1-dimethyl-3-hydroxyethyl-9'-methoxyspiro[benz[e]-indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 3,3-dimethyl-1-hydroxyethyl-9'-methoxyspiro[benz[g]-indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 3-carboxyethyl-1,1-dimethyl-9'-methoxyspiro[benz[e]-indolin-2,3'-[3H]-pyrido[2,1-b][1,4]benzoxazine];1-Carboxyethyl-3,3-dimethyl-9'-methoxyspiro[benz[g]-indolin-2,3'-[3H]-pyrido[2,1-b][1,4]benzoxazine]; 1,1-dimethyl-3-hydroxyethyl-9'-methoxyspiro[benz[e]-indolin-2,3'-[3H]-pyrido[2,1-b][1,4]benzoxazine]; 3,3-dimethyl-1-hydroxyethyl-9'-methoxyspiro[benz[g]-indolin-2,3'-[3H]-pyrido[2,1-b][1,4]benzoxazine]; A method comprising: 5-amino-5'-(2-benzthiazolyl)-1,3,3-trimethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 5-amino-5'-(5'-(2-hydroxyphenyl)-2-oxadiazolyl)-1-isopropyl-3,3-dimethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 5-amino-5'-(5'-phenyl-2-oxadiazolyl)-1,3,3-trimethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; or a mixture thereof.;

[0303] 63. In Embodiment 58 or Embodiment 59, the reactive photochromic compound is 3,3-bis(4-methoxyphenyl)-6,11-dimethyl-13-hydroxyethoxy-13-phenyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-bis(4-methoxyphenyl)-6,11-dimethyl-13-(2-hydroxycarbonylethyl)carboxyethoxy-13-phenyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-bis(4-methoxyphenyl)-6,11-dimethyl-13-hydroxy-13-phenyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; or a method that is a mixture of these.

[0304] 64. A method in any one of embodiments 1 to 63, wherein the at least one first and second polymerizable material independently comprises at least one polymerizable UV / HEVL absorbing compound.

[0305] 65. A method in any one of embodiments 1 to 64, wherein the first polymerizable fluid composition further comprises at least one visible light free radical photoinitiator, and the droplet of the first polymerizable fluid composition is irradiated with visible light for about 10 seconds or less before dispensing the second polymerizable fluid composition.

[0306] 66. A method according to Embodiment 65, wherein one or more visible light free radical photoinitiators comprise a benzoylphosphine initiator and / or an acylgermanium photoinitiator.

[0307] 67. In Embodiment 65, the at least one first free radical photoinitiator is , , or A method comprising an acyl-germanium photoinitiator.

[0308] 68. Method in Embodiment 66 or Embodiment 67, wherein the visible light is visible light in the range of 420 nm to 500 nm.

[0309] 69. A method in any one of embodiments 65 to 68, wherein a droplet of the first polymerizable fluid composition is irradiated with visible light for about 8 seconds or less.

[0310] 70. A method in any one of embodiments 65 to 68, wherein a droplet of the first polymerizable fluid composition is irradiated with visible light for about 5 seconds or less.

[0311] 71. A hydrogel contact lens obtained according to any one of the methods of Embodiments 1 to 70.

[0312] The present disclosure will enable those skilled in the art to practice the invention. Various modifications, variations, and combinations of the various embodiments described herein may be made. To enable the reader to better understand specific embodiments and their benefits, it is suggested to refer to the following examples. The present specification and examples are intended to be regarded as exemplary.

[0313] Example 1

[0314] Oxygen permeability measurement

[0315] Unless otherwise specified, oxygen permeability (Dk / t) of the lens and lens material, intrinsic (or edge-corrected) oxygen permeability (Dk i or Dk c ) is measured according to the procedure described in ISO 18369-4.

[0316] Equilibrium water content

[0317] The equilibrium water content (EWC) of a contact lens is determined as follows.

[0318] Determine the amount of water (expressed as weight percent) present in a fully equilibrated, hydrated hydrogel contact lens in a saline solution at room temperature. Quickly stack the lenses, blot them with a cloth, and then transfer the lens stack to an aluminum pan on a chemical balance. The number of lenses for each sample pan is typically five. Record the hydrated weight of the pan + lens. Cover the pan with aluminum foil. Place the pan in a laboratory oven at 100±2°C and dry it for 16 to 18 hours. Remove the pan + lens from the oven and cool it in a dryer for at least 30 minutes. Remove a single pan from the dryer and discard the aluminum foil. Weigh the pan + dried lens sample on a chemical balance. Repeat for all pans. The wet and dry weights of the lens sample can be calculated by subtracting the weight of the empty weighing pan.

[0319] Elastic modulus

[0320] The elastic modulus of a contact lens is measured using the MTS insight instrument. The contact lens is first cut into a 3.12 mm wide strip using a Precision Concept 2 stage cutter. Five thickness values ​​are measured within a 6.5 mm gauge length. The strip is mounted on the instrument grip and immersed in PBS (phosphate-buffered saline) at a controlled temperature of 21 ± 2°C. Typically, a 5 N load cell is used for the test. A constant force and velocity are applied to the sample until the sample fractures. Force and displacement data are collected by TestWorks software. The elastic modulus value, which is the slope or tangent of the stress-strain curve at an elongation close to zero in the elastic deformation region, is calculated using TestWorks software.

[0321] chemical substances

[0322] PrOH represents 1-propanol; TAA represents tert-amyl alcohol; EtOAc represents ethyl acetate; DMA represents N,N-dimethylacrylamide; MMA represents methyl methacrylate; EGMA represents ethylene glycol methyl ether methacrylate; TEGDMA represents triethylene glycol dimethacrylate; D6 represents monobutyl-terminated monomethacryloxypropyl-terminated polydimethylsiloxane (Mw approx. 750 g / mol, Shin-Etsu); GA represents a hydrophilic polysiloxane vinyl crosslinker of formula G (Mn approx. 6.8K g / mol, OH content approx. 1.2 meq / g, Shin-Etsu); The "G4" macromonomer represents the di-methacryloyloxypropyl-terminated polysiloxane of the above formula A (Mn approx. 13.5 K g / mol, OH content approx. 1.8 meq / g); Vazo 64 represents 2,2'-dimethyl-2,2'azodipropiononitrile; Nobloc is Aldrich's 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl methacrylate; Norbloc is Aldrich's 2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole; NPD-blue represents a polymerizable naphthopyran photochromic dye that exhibits blue in the activated state (Vivimed); NPD-green represents a polymerizable naphthopyran photochromic dye that exhibits green in the activated state (Vivimed); RB247 is Reactive Blue 247.

[0323] [Chemical Formula G]

[0324]

[0325] Example 2

[0326] Polymerizable composition

[0327] Two polymerizable compositions for forming a silicone hydrogel material are prepared by blending all essential components to have the compositions shown in Tables 1 and 2.

[0328]

[0329]

[0330] Fabrication of SiHy contact lenses with a central photochromic zone

[0331] Formulation 2A is purged with nitrogen at room temperature for 30 to 35 minutes. About 3 μL of Formulation 2A is administered to the geometric center of the molding surface of the male (BC) mold half (made of polypropylene) of a plastic mold (power: -3.0) to form a droplet at the geometric center of the molding surface of the male mold half.

[0332] Formulation 2B is purged with nitrogen at room temperature for 30 to 35 minutes. About 60 μL of N2-purged Formulation 2B is added to the molding surface of the female (FC) mold half, and then the mold is closed with the male (BC) mold half to which the droplet is attached to form a molded assembly containing droplets of Formulation 2B and Formulation 2A.

[0333] The molded assembly is heat-cured in an oven according to the following curing profile: ramping from room temperature to 55°C at a ramp rate of about 7°C / min; holding at 55°C for about 30 minutes; ramping from 55°C to 80°C at a ramp rate of about 7°C / min; holding at 80°C for about 30 minutes; ramping from 80°C to 100°C at a ramp rate of about 7°C / min; and holding at 100°C for about 30 minutes.

[0334] After demolding, the cast-molded SiHy contact lens is extracted with PrOH for 180 minutes and then rinsed in PB (phosphate buffer containing about 0.077 wt% NaH2PO4·H2O and about 0.31 wt% Na2HPO4·2H2O) for 1 hour.

[0335] All publications and patents cited above in this application are incorporated herein by reference in their entirety.

Claims

Claim 1 A method for manufacturing a hydrogel contact lens, comprising: (1) obtaining a first polymerizable fluid composition and a second polymerizable fluid composition, wherein the first polymerizable fluid composition comprises at least one first free radical initiator, at least one first polymerizable material, and at least one photochromic compound, wherein the at least one first polymerizable material comprises at least one first polysiloxane vinyl crosslinking agent having a weight average molecular weight of 5000 daltons or more and present in the first polymerizable composition in an amount of 40 weight% or more, and the second polymerizable fluid composition comprises at least one second free radical initiator and at least one second polymerizable material and is free of any photochromic compound; (2) obtaining a lens mold comprising a male mold half having a first molding surface defining the rear surface of the contact lens to be molded and a female mold half having a second molding surface defining the front surface of the contact lens to be molded, wherein, upon mold closing, the female and male mold halves accommodate each other so that the mold is formed between the first and second molding surfaces A step of obtaining a lens mold configured to form a cavity; (3) a step of applying a droplet of a first polymerizable fluid composition onto the geometric center of a first molding portion of a male mold half, wherein the volume of the droplet is 5 μL or less; (4) a step of dispensing a predetermined amount of a second polymerizable fluid composition onto a second molding surface of a female mold half; (5) a step of closing the female mold half with the male mold half to which the droplet is attached to form a molded assembly comprising the droplet of the second polymerizable composition and the first polymerizable composition within the mold cavity; (6) a step of curing the droplet of the second polymerizable fluid composition and the first polymerizable composition to form a raw silicone hydrogel contact lens having a photochromic central region, wherein the photochromic central region has a diameter of 13 mm or less and is concentric with the central axis of the raw silicone hydrogel contact lens;(7) a step of separating a molded assembly into a male mold half and a female mold half with a raw silicone hydrogel contact lens attached to a lens-attached mold half, which is one of the male and female mold halfs; (8) a step of removing the raw silicone hydrogel contact lens from the lens-attached mold half; and (9) a step of applying the raw silicone hydrogel contact lens to a post-molding process comprising a hydration process and one or more other processes selected from the group consisting of extraction, surface treatment, packaging, sterilization, and combinations thereof.; Claim 2 In claim 1, the curing step of (6) is performed thermally, and the at least one first and second free radical initiator comprises a thermal free radical initiator. Claim 3 A method according to claim 1, wherein the curing step of (6) is performed by a chemical line, and the at least one first and second free radical initiator comprises a free radical photoinitiator. Claim 4 A method according to claim 1, wherein the first polymerizable fluid composition further comprises at least one visible light free radical photoinitiator, and a droplet of the first polymerizable fluid composition is irradiated with visible light for 10 seconds or less before dispensing the second polymerizable fluid composition. Claim 5 In claim 1, the at least one first and second polymerizable material comprises, independently of each other, at least one component selected from the group consisting of (a) at least one silicon-containing vinyl monomer, (b) at least one second polysiloxane vinyl crosslinker, at least one non-silicon vinyl crosslinker, or a combination thereof, (c) at least one hydrophilic vinyl monomer, and optionally (d) a non-silicon hydrophobic vinyl monomer, a UV-absorbing vinyl monomer, and a combination thereof, wherein the at least one hydrophilic vinyl monomer comprises (i) at least one hydrophilic (meth)acrylamido monomer having 3 to 8 carbon atoms; (ii) at least one hydrophilic (meth)acryloxy monomer; (iii) at least one hydrophilic N-vinylamide monomer; or (iv) comprising a combination thereof, wherein the at least one silicon-containing vinyl monomer comprises (i) at least one silicon-containing vinyl monomer containing a single ethylene-based unsaturated group selected from the group consisting of a tris(trialkylsiloxy)silyl group, and a (meth)acryloyloxy group, (meth)acryloylamino group, vinyl carbonate group, and vinyl carbamate group; (ii) at least one silicon-containing vinyl monomer containing a single ethylene-based unsaturated group selected from the group consisting of a bis(trialkylsilyloxy)-alkylsilyl group, and a (meth)acryloyloxy group, (meth)acryloylamino group, vinyl carbonate group, and vinyl carbamate group; (iii) a) one single ethylene-based unsaturated group selected from the group consisting of (meth)acryloyloxy groups, (meth)acryloylamino groups, vinyl carbonate groups, and vinyl carbamate groups, and b) at least a silicon-containing vinyl monomer comprising a polysiloxane chain having 2 to 30 siloxane units and terminated by an alkyl, hydroxyalkyl, or methoxyalkyl group; or (iv) a combination thereof, comprising a method. Claim 6 A method according to claim 5, wherein the sum of the amounts of components (a), (b), and (c) in the monomer mixture is at least 60% by weight relative to the total weight of all polymerizable materials present in the monomer mixture. Claim 7 A method according to claim 5, wherein the at least one first and second polymerizable material independently comprises at least one second polysiloxane vinyl crosslinking agent. Claim 8 A method according to any one of claims 1 to 7, wherein the at least one first and second polymerizable material comprises, independently of each other, at least one non-silicon vinyl crosslinking agent; at least one non-silicon hydrophobic vinyl monomer; at least one UV-absorbing vinyl monomer; or a combination thereof. Claim 9 In any one of claims 1 to 7, the at least one photochromic compound is naphtopyran, indeno-fused naphtopyran, heterocyclic ring-fused naphtopyran, benzopyran, phenantropyran, quinopyran, quinolinopyran, fluoroantenopyran, anthracene-fused pyran, tetracene-fused pyran, spiro(benzindolin)naphtopyran, spiro(indolin)naphtopyran, spiro(indolin)benzopyran, spiro(indolin)quinopyran, spiro(indolin)pyran, naphthoxazine, spirobenzopyran, spirobenzothiopyran, naphthacenedione, benzoxazine, spirooxazine, naphthoxazine, spiro(benzindolin)naphthoxazine, spiro(indolin)naphthoxazine, spiro(indolin)pyrido-benzoxazine, Spiro(indoline)benzoate, Spiro(benzindolin)benzoate, Spiro(benzindolin)pyridobenzoate, Spiro(indoline)fluolanthenox, Spiro(indoline)quinox, Spiropiperidine-naphtopyran, Pyro(indoline)pyronobenzoate, Benzospiropyran, Naphtospiropyran, Spirobenzoate-pyrrolopyridine, Spironaftox-pyrrolopyridine, Spiro-oxazepine-benzoate, Spiro(indoline)benzophyrolox, Spiro(indoline)quinazolino-oxoate, Spiro(indoline)anthracenobenzoate, Benzofurobenzopyran, Benzothienobenzopyran, A method comprising naphthofurobenzopyran, benzopyrano-fused naphthofyran, spiro(isoindoline)-naphtoxazine, spiro(isoindoline)benzoxazine, or a mixture thereof. Claim 10 A method according to claim 9, wherein at least one photochromic compound is polymerizable and comprises an ethylene-based unsaturated group. Claim 11 In claim 10, the at least one photochromic compound is a coupling reaction product of a reactive (meth)acrylamido or (meth)acryloxy monomer having a first reactive functional group and a reactive photochromic compound having a second reactive functional group in the absence or presence of a coupling agent in a coupling reaction, wherein the first reactive functional group is -COCl, -COBr, -COOH, -NHR N2 , -NCO, -OH, -CHO, , , or Selected from the group consisting of, and the second reactive functional group is -COOH, -NHR N2 , , , , -NCO, -OH, -SH, -CHO, , , or Selected from the group consisting of, where R0 is hydrogen or methyl and R N2 is hydrogen, linear or branched C1-C 15 A method in which alkyl, cyclohexyl, cyclopentyl, substituted or unsubstituted phenyl, or substituted or unsubstituted phenyl-C1-C6 alkyl. Claim 12 In claim 11, the reactive (meth)acrylamido or (meth)acryloxy monomer is a (meth)acryloyl halide in which CH2=CH─COX or CH2=CCH3─COX, where X=Cl or Br, N-hydroxysuccinimide ester of (meth)acrylic acid, glycidyl (meth)acrylate, isocyanato-C2-C6 alkyl (meth)acrylate, amino-C2-C6 alkyl (meth)acrylamide, C1-C6 alkylamino-C2-C6 alkyl (meth)acrylamide, (meth)acrylic acid, C2-C4 alkylacrylic acid, N-2-acrylamidoglycolic acid, 3-(acryloyloxy)propanoic acid, C2-C6 hydroxylalkyl (meth)acrylate, C2-C6 hydroxyalkyl (meth)acrylamide, azlactone-containing vinyl Monomer, aziridinyl C1-C 12 A method selected from the group consisting of alkyl (meth)acrylates, acrolein, metacrolein, crotonaldehyde, and combinations thereof. Claim 13 In paragraph 12, the reactive photochromic compound is 3,3-bis(4-methoxyphenyl)-6,11-dimethyl-13-hydroxyethoxy-13-phenyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-bis(4-methoxyphenyl)-6,11-dimethyl-13-(2-hydroxycarbonylethyl)carboxyethoxy-13-phenyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-bis(4-methoxyphenyl)-6,11-dimethyl-13-hydroxy-13-phenyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-Bis(4-methoxyphenyl)-6,11-dimethyl-13-(2-hydroxycarbonylethyl)carboxy-13-phenyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-Bis(4-methoxyphenyl)-6,11-dimethyl-13-hydroxy-13-propyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-Bis(4-methoxyphenyl)-6,11-dimethyl-13-(2-hydroxycarbonylethyl)carboxy-13-propyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-10,11-dimethoxy-13-hydroxy-13-ethyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-10,11-dimethoxy-13-(2-hydroxycarbonylethyl)carboxy-13-ethyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-bis(4-methoxyphenyl)-7-methoxy-11-phenyl-13-hydroxymethyl-13-methyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-Bis(4-methoxyphenyl)-7-methoxy-11-phenyl-13-(2-hydroxycarbonylethyl)carboxymethyl-13-methyl-3H,13H-indeno[2',3':3,4]-naphtho[1,2-b]pyran; 3,3-Bis(4-methoxyphenyl)-7-methoxy-11-phenyl-13-hydroxy-13-methyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;3,3-Bis(4-methoxyphenyl)-7-methoxy-11-phenyl-13-(2-hydroxycarbonylethyl)carboxy-13-methyl-3H,13H-indeno-[2',3':3,4]naphtho[1,2-b]pyran; 3,3-Bis(4-methoxyphenyl)-11-phenyl-13-hydroxy-13-methyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-Bis(4-methoxyphenyl)-11-phenyl-13-(2-hydroxycarbonylethyl)carboxy-13-methyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-6,7,10,11-tetramethoxy-13-hydroxy-13-ethyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-bis(4-methoxyphenyl)-6,7,10,11-tetramethyl-13-(2-hydroxycarbonylethyl)carboxy-13-methyl-3H,13H-indeno[2',3':3,4]-naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-6,7-dimethoxy-13-hydroxy-13-ethyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-bis(4-methoxyphenyl)-11-(4-(4,5-diphenyl-1H-imidazole-2-yl)phenyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-6-methoxy-7-(3-hydroxymethylenepiperidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1.2-b]pyran; 3,3-di(4-methoxyphenyl)-6-methoxy-7-(3-(2-hydroxycarbonylethyl)-carboxymethylenepiperidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-6,7-dimethoxy-13-hydroxy-13-butyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-6,11,13-trimethyl-13-(2-(2-hydroxyethoxy)-ethoxy)-indeno[2,1-f]naphtho[1,2-b]pyran;3,3-di(4-methoxyphenyl)-6,11,13-trimethyl-13-(2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)ethoxy)-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-diphenyl-13-hydroxy-13-(2-oxo-2-ethoxyethyl)-1H-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-6,11-dimethyl-13-hydroxy-13-(2-oxo-2-ethoxyethyl)-1H-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-6,11-dimethyl-13-butyl-13-hydroxy-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-bis(4-hydroxyphenyl)-7-methoxy-11-phenyl-13,13-diethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-bis(4-hydroxyphenyl)-7-methoxy-11-phenyl-13,13-dipropyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-Bis(4-hydroxyphenyl)-7-methoxy-11-phenyl-13-carbomethoxy-13-methyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-diphenyl-6,7-dimethoxy-13-methyl-13-methyl-13-hydroxyethoxyethoxy-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-diphenyl-6,7,10,11-tetramethoxy-13-ethyl-13-methyl-13-hydroxyethoxyethoxy-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 6,7-Dimethoxy-2,2-Diphenyl-13-hydroxy-13-butyl-2H,13H-Indeno[1',2':4,3]Naphtho[1,2-b]pyran; 6,7-Dimethoxy-2,2-Diphenyl-13-hydroxy-13-methyl-2H,13H-Indeno[1',2':4,3]Naphtho[1,2-b]pyran; 6,7-Dimethoxy-2,2-Diphenyl-13-hydroxy-2H,13H-Indeno[1',2':4,3]Naphtho[1,2-b]pyran; 3-(4-allyloxyphenyl)-3-(4-morpholinophenyl)-7-methoxy-11-phenyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;3-(4-fluorophenyl)-3-(4-butoxyphenyl)-10-(piperazine-1-yl)-6-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3:4]naphtho[1,2-b]pyran; 3-(4-fluorophenyl)-3-(4-butoxyphenyl)-10-(4-hydroxybenzamido)-6-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3:4]naphtho[1,2-b]pyran; 3-(4-fluorophenyl)-3-(4-butoxyphenyl)-10-vinyl-6-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3:4]naphtho[1,2-b]pyran; 3-(4-fluorophenyl)-3-(4-butoxyphenyl)-10-(carboxylic acid)-6-trifluoromethyl-13,13-dimethyl-3H,13H-indeno[2',3':3:4]naphtho[1,2-b]pyran; 3-(4-fluorophenyl)-3-(4-methoxyphenyl)-6-methoxy-7-(4-hydroxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-(4-fluorophenyl)-3-(4-methoxyphenyl)-6-methoxy-7-(4-(2-hydroxycarbonylethyl)carboxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-(4-fluorophenyl)-3-(4-morpholinophenyl)-6-methoxy-7-(4-hydroxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1.2-b]pyran; 3-(4-fluorophenyl)-3-(4-morpholinophenyl)-6-methoxy-7-(4-(2-hydroxycarbonylethyl)carboxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-(4-hydroxyethoxyphenyl)-3-(4-methoxyphenyl)-11-(4-(N,N-dimethylamino)phenyl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(2,4-dimethoxyphenyl)-phenyl-6,11-dimethoxy-13-methyl-13-methyl-13-hydroxyethoxyethoxyethoxy-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran;3-(4-methoxyphenyl)-3-(3-methyl-4-methoxyphenyl)-13-hydroxy-indeno[2,1-f]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6,7,10,11-tetramethoxy-13-hydroxy-13-ethyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6,7,10,11-tetramethoxy-13-hydroxy-13-butyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6,7-dimethoxy-13-hydroxy-13-ethyl-3H,13H-deno[2,1-f]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6,7-dimethoxy-13-hydroxy-13-methyl-3H,13H-deno[2,1-f]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-13-oxo-3H,13H-deno[2,1-f]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-phenyl-6-methoxy-7-morpholino-13-methyl-13-methyl-13-hydroxyethoxyethoxyethoxy-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-phenyl-6,11-dimethoxy-13-methyl-13-methyl-13-hydroxyethoxy-ethoxy-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 2-(4-methoxyphenyl)-2-(4-morpholinophenyl)-5-hydroxy-6-carboethoxy-2H-naphtho[1,2-b]pyran; 3-(4-morpholinophenyl)-3-phenyl-6,7-dimethoxy-13-hydroxy-13-ethyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3-(4-morpholinophenyl)-3-phenyl-6,7-dimethoxy-13-hydroxy-13-butyl-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran; 3-(4-morpholinophenyl)-3-phenyl-6,7-dimethoxy-13-oxo-3H,13H-indeno[2,1-f]naphtho[1,2-b]pyran;3-phenyl-3-(4-hydroxyethoxyphenyl)-6-methoxy-7-morpholino-13,13-dimethyl-3H,13H-indeno-[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(2-hydroxycarbonylethyl)carboxyethoxy-phenyl)-6-methoxy-7-morpholino-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(2-hydroxyethoxy)phenyl)-6-methoxy-7-piperidino-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(2-(2-hydroxycarbonylethyl)-carboxyethoxy)phenyl)-6-methoxy-7-piperidino-13,13-dimethyl-3H,13H-indene[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-hydroxyphenyl)-6,7-dimethoxy-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-hydroxyethoxy)phenyl)-6,7-dimethoxy-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(2-hydroxycarbonylethyl)carboxyethoxy)phenyl)-6,7-dimethoxy-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(2-hydroxycarbonylethyl)carboxy-phenyl)-6,7-dimethoxy-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(4-(2-hydroxyethyl)piperazine-1-yl)phenyl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(4-(2-(2-hydroxycarbonylethyl)-carboxyethyl)piperazine-1-yl)phenyl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho-[1,2-b]pyran; 3-phenyl-3-(4-methoxyphenyl)-6-methoxy-7-piperazinyl-13,13-dimethyl-3H,13H-indene[2',3':3,4]naphtho[1,2-b]pyran;3-phenyl-3-(4-methoxyphenyl)-6-methoxy-7-(3-hydroxymethylenepiperidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3":3.4]naphtho[1.2-b]pyran; 3-phenyl-3-(4-methoxyphenyl)-6-methoxy-7-(3-(2-hydroxycarbonylethyl)carboxymethylenepiperidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3":3.4]naphtho[1.2-b]pyran; 3-phenyl-3-(4-methoxyphenyl)-6-methoxy-7-(4-hydroxypifenidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho-[1,2-b]pyran; 3-phenyl-3-(4-methoxyphenyl)-6-methoxy-7-(4-(2-hydroxycarbonylethyl)-carboxypifenidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(4-methoxyphenyl-piperazine-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-hydroxy-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(4-methoxyphenyl-piperazine-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(2-hydroxy-2-methyl-3-butin-4-yl)-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-morpholinophenyl)-6-methoxy-7-(3-hydroxymethylene-piperidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho-[1,2-b]pyran; 3-phenyl-3-(4-morpholinophenyl)-6-methoxy-7-(3-(2-hydroxycarbonyl-ethyl)carboxymethylene-piperidine-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3.4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-morpholinophenyl)-6-methoxy-7-(3-(2-hydroxycarbonylethyl)carboxymethylene-piperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-morpholinophenyl)-6-methoxy-7-(4-hydroxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1.2-b]pyran;3-phenyl-3-(4-morpholinophenyl)-6-methoxy-7-(4-(2-hydroxycarbonylethyl)-carboxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-morpholinophenyl)-6-methoxy-7-piperazinyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-morpholinophenyl)-6,11-dimethyl-13-hydroxy-13-(1-oxo-methoxyprop-2-yl)-1H-indeno[2,1-f]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(4-phenylpiperazino)-phenyl)-6-methoxy-7-(4-hydroxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1.2-b]pyran; 3-phenyl-3-(4-(4-phenylpiperazino)phenyl)-6-methoxy-7-(4-(2-hydroxycarbonylethyl)carboxypiperidin-1-yl)-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1.2-b]pyran; 3-phenyl-3-(4-piperazinylphenyl)-6,11-dimethoxy-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho-[1,2-b]pyran; 3-phenyl-3-(4-piperazinylphenyl)-6-methoxy-7-piperidinyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-(3-methylpiperazine-1-yl)phenyl)-6-methoxy-7-(decahydroisoquinoline-2-yl)-11-tert-butyl-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-16-(ethoxycanobyl)methyl-16-hydroxy-3,16-dihydrobenzofuro-[2',3':7,8]indeno[2',3':3,4]naphtho[1,2-b]pyran; 3-phenyl-3-(4-methoxyphenyl)-16-(ethoxycanobyl)-methyl-16-hydroxy-3,16-dihydrobenzofuro-[2",3":6',7']indeno-[3',2':4,3]naphtho[1,2-b]pyran;3-phenyl-3-(4-morpholinophenyl)-16-(ethoxycanobyl)-methyl-16-hydroxy-3,16-dihydrobenzofuro[2',3':6',7']deno[3',2':4,3]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-16-(ethoxycarbonyl)methyl-16-hydroxy-3,16-dihydrobenzofuro[2',3':7,8]deno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-16-hydroxy-16-ethyl-16H-benzofuro[2',3':7,8]indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-16-hydroxy-16H-benzofuro[2",3":6,7]indeno[3',2':4,3]naphtho-[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-16-hydroxy-16-ethyl-16H-benzofuro[2",3":6,7]-indeno[3',2':4,3]naphtho[1,2-b]pyran; A method comprising 3-(4-methoxyphenyl)-3-(2,3-dihydrobenzofuro-5-yl)-13-hydroxy-13-methyl-indeno[2,1-f]naphtho[1,2-b]pyran; 3-(4-methoxyphenyl)-3-(2,3-dihydrobenzofuro-5-yl)-6,11-difluoro-13-hydroxy-13-(1-oxo-methoxyprop-2-yl)-1H-indeno[2,1-f]naphtho[1,2-b]pyran, or a mixture thereof.; Claim 14 In paragraph 12, the reactive photochromic compound is 2,2-di(4-fluorophenyl)-5-hydroxycarbonyl-6-phenyl-9-methoxy-2H-naphtho[1,2-b]pyran; 2,2-bis(4-methylphenyl)-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-methoxycarbonyl-6-hydroxy-[2H]-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-methoxyethoxycarbonyl-6-methyl-8-vinyl-2H-naphtho[1,2-b]pyran; 2,2-Bis(4-methoxyphenyl)-5-methoxyethoxycarbonyl-6-methyl-8-hydroxycarbonyl-2H-naphtho[1,2-b]pyran; 2,2-Bis(4-methoxyphenyl)-5-methoxycarbonyl-6-(2-hydroxyethoxy)ethoxy-[2H]-naphtho[1,2-b]pyran; 2,2-Bis(4-methoxyphenyl)-5-methoxycarbonyl-6-phenyl-9-(2-hydroxyethoxy)-[2H]-naphtho[1,2-b]pyran; 2,2-Bis(4-methoxyphenyl)-5-methoxy-carbonyl-6-(4-(2-hydroxyethoxy)phenyl)-[2H]-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-diphenylmethylol-6-hydroxy-2H-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-diphenylmethylol-6-methoxy-2H-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-(2-hydroxyethoxylcarbonyl)-6-phenyl-[2H]-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-(2-(2-hydroxyethoxy)-ethoxycarbonyl)-6-phenyl-[2H]-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-(2-(2-(2-hydroxyethoxy)ethoxy)-ethoxycarbonyl)-6-phenyl-[2H]-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-(2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)-ethoxycarbonyl)-6-phenyl-[2H]-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-hydroxymethyl-6-methyl-9-methoxy-2H-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-hydroxymethyl-6-phenyl-2H-naphtho[1,2-b]pyran;2,2-bis(4-methoxyphenyl)-5-hydroxymethyl-6-methoxy-2H-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-methoxycarbonyl-6-(3-aminophenyl)-2H-naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-2,5,7-trihydro-7-methylidine-5-oxo-furo-[3',4':3,4]naphtho[1,2-b]pyran; 2,2-bis(4-methoxyphenyl)-5-phenylthio-6-hydroxy-2H-naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-13-hydroxy-13-methyl-indeno[2,1-f]naphtho[1,2-b]pyran; 3,3-di(4-methoxyphenyl)-9-methoxycarbonyl-8-(2-hydroxyethoxy)ethoxy-[3H]-naphtho[1,2-b]pyran; 2,2-diphenyl-5-hydroxycarbonyl-9-methoxy-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-5-hydroxycarbonyl-8,9-dimethoxy-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-5-hydroxy-6-carboethoxy-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-5-hydroxy-6-morpholinocarbonyl-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-5-hydroxy-6-carboethoxy-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-5-hydroxy-6-carbomethoxy-9-methoxy-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-5-hydroxy-6-morpholinocarbonyl-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-5-methylol-6-(3-dimethylaminopropyl)-methylamino-2H-naphtho[1,2-b]pyran; 2,2-diphenyl-2,5,7-trihydro-7-methylidene-5-oxofuro-[3',4':3,4]naphtho[1,2-b]pyran; 2,2-spiroadamantylene-5-phenylthio-6-hydroxy-2H-naphtho[1,2-b]pyran; 2,2-diphenyl)-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 2,2-spiro-admamtylene-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran, 3,3-diphenyl-8-hydroxy-9-carbopropoxy-3H-naphtho[2,1-b]pyran; 2,2,5-triphenyl-6-carboethoxy-2H-naphtho[1,2-b]pyran;2,2,6-triphenyl-5-(2-(2-(2-(2-hydroxyethoxy)ethoxy)-ethoxy)ethoxy)carbonyl-[2H]-naphtho[1,2-b]pyran; 2,2,6-triphenyl-5-(2-(2-(2-oxiran-2-ylmethoxy)ethoxy)ethoxy)-ethoxycarbonyl)-[2H]-naphtho[1,2-b]pyran; 2-(4-methoxyphenyl)-2-(4-morpholinophenyl)-5-hydroxy-6-carboethoxy-2H-naphtho[1,2-b]pyran; 2-(4-methoxyphenyl)-2-tert-butyl-5-methoxy-carbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 2-(4-methoxyphenyl)-2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 2-(4-(2-(2-hydroxyethoxy)ethoxy)-ethoxyphenyl)-2-phenyl-5-methoxycarbonyl-6-methyl-9-methoxy-[2H]-naphtho[1,2-b]pyran; 2-(4-(2-(2-hydroxyethoxy)ethoxy)phenyl)-2-phenyl-5-methoxycarbonyl-6-(2-(2-methylprop-2-enoxyloxy)ethoxy)-[2H]-naphtho[1,2-b]pyran; 3-(4-(2-(2-hydroxyethoxy)-ethoxy)ethoxyphenyl)-3-phenyl-9-methoxycarbonyl-8-methoxy-[3H]-naphtho[1,2-b]pyran; 2-(4-morpholinophenyl)-2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 2-(9-ethylcarbazole-2-yl)-2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 2-(9-phenylcarbazole-2-yl)-2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 2-(4-dimethylaminophenyl)-2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1,2-b]pyran; 3-(2-fluorophenyl)-3-(4-methoxyphenyl-8-hydroxy-9-carbopropoxy-3H-naphtho[2,1-b]pyran; 3-(2-fluorophenyl)-3-(4-methoxyphenyl-8-hydroxy-9-carbomethoxy-3H-naphtho[2,1-b]pyran; 3-(2,4-dimethoxyphenyl)-3-(4-methoxyphenyl-8-hydroxy-9-carbomethoxy-3H-naphtho[2,1-b]pyran; 3-(2,4,6-trifluorophenyl)-3-(2,4,6-trimethoxy-1-naphthyl)-8-acetyl-9-carbonylloyl-3H-naphtho[2,1-b]pyran;3-(4-methoxyphenyl)-3-(2-methyl-2,3-dihydrobenzofuro-5-yl)-6-methoxy-12-hydroxymethyl-11-phenyl-3H-phenantro[1,2-b]pyran; 5,5-bis(4-methoxyphenyl)-8-methylol-5H-fluoranteno[3,2-b]pyran; or a mixture thereof, a method.; Claim 15 In paragraph 12, the reactive photochromic compound is 1-hydroxyethyl-3,3-dimethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1-hydroxypropyl-3,3-dimethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1-aminoethyl-3,3-dimethyl-5-chlorospiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1-hydroxyethyl-3,3-dimethyl-8'-methoxyspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1-(p-vinylphenyl)-3,3-dimethyl-5,6-dichlorospiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1,3,3-trimethyl-9'-hydroxyspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1,3,3-trimethyl-5'-hydroxymethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1,3,3-trimethyl-9'-aminospiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1,3,3-trimethyl-5-chloro-8'-hydroxyspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1-benzyl-3,3-dimethyl-9'-vinylbenzoyoxyspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1-benzyl-3,3-dimethyl-5'-hydroxymethylpiperidinospironaphthooxazine; 1,3,3-trimethyl-9'-hydroxyspiro[indolin-2,3'-[3H]-pyrido-[2,1-b][1,4]benzoxazine]; 5-hydroxy-6'-cyano-1,3,3-trimethyl-spiro-[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 5-hydroxy-6'-phenylsulfonyl-1,3,3-trimethyl-spiro-[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 5'formyl-1,3,3-trimethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine; 1,3-dihydro-6'-piperazino-1,3,3-trimethylspiro[2H indole-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine;1,3-Dihydro-6'-(4-hydroxyethyl)piperazino-1,3,3-trimethylspiro[2H indole-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine; 1,3-Dihydro-9'-hydroxy-1,3,3-trimethylspiro[2H indole-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine; 1,3,3,4,5-pentamethyl-9'-methoxycarbonyl-8'-hydroxy-spiro[indolin-2,3'-[3H]naphtho[2,1-b][1,4]oxazine; 1,3,3,5,6-pentamethyl-9'-methoxycarbonyl-8'-hydroxy-spiro[indolin-2,3'-[3H]napt[2,1-b][1,4]oxazine; 1-propyl-3,3,4,5-tetramethyl-9'-methoxycarbonyl-8'-hydroxy-spiro[indolin-2,3'-[3H]napt[2,1-b][1,4]oxazine; 1-propyl-3,3,5,6-tetramethyl-9'-methoxycarbonyl-8'-hydroxy-spiro[indolin-2,3'-[3H]napt[2,1-b][1,4]oxazine; 1-Methoxyethyl-3,3-Dimethyl-9'-Allyloxycarbonyl-8'-Chloroactoxy-spiro[Indolin-2,3'-[3H]Napt[2,1-b][1,4]Oxazine; 1-Allyl-3,3-Spirocyclohexyl-9'-Benzyloxycarbonyl-8'-Chloroactoxy-spiro[Indolin-2,3'-[3H]Napt[2,1-b][1,4]Oxazine; 5-Amino-1,3,3-Trimethyl-spiro[Indolin-2,3'-[3H]-Pyrido[3,4-f][1,4]-Benzoxazine; 6-Hydroxy-1',3',3',4',5'-Pentamethylspiro[2H-1,4-Benzoxazine-2,2'-Indolin]; 6-hydroxy-1',3',3',5',6'-pentamethylspiro[2H-1,4-benzoxazine-2,2'-indolin]; 5,7-dimethoxy-1'-hydroxy-carbonylethyl-3',3'-dimethylspiro[2H-1,4-benzoxazine-2,2'-indolin]; 7-methoxy-1'-hydroxy-ethyl-3',3'-dimethylspiro[2H-1,4-benzoxazine-2,2'-indolin]; 9'-hydroxy-1-methylspiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine]; 5-chloro-9'-hydroxy-1-methylspiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine];8'-hydroxy-1-methylspiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine]; 8'-hydroxy-5-methoxy-1-methylspiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine]; 8'-hydroxy-1,4,5-trimethylspiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine]; 9'-hydroxy-1-isopropylspiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine]; 9'-hydroxy-1-hexadecyl-spiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine]; 9'-hydroxy-1-octadecylspiro[indolin-2,3'-(3H)-naphtho(2,1-b)-1,4-oxazine]; 1,1"-(1,5-pentanediyl)bis[3,3-dimethyl]-9'-hydroxy-spiro[indolin-2,3'-[3H]-naphtho[2,1-b] [1,4]oxazine]; 1,1"-[1,4-phenylenebis(methylene)]bis[3,3-dimethyl]-5'-hydroxymethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b] [1,4]oxazine]; 1,1"-(1,4-butanediyl)bis[5,6-dichloro-3,3-dimethyl]-8'-hydroxyspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1,3,3-trimethyl-9'-hydroxypiperidinospyronafthoxazine; 3-carboxyethyl-1,1-dimethyl-9'-methoxyspiro[benz[e]-indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1-carboxyethyl-3,3-dimethyl-9'-methoxyspiro[benz[g]-indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 1,1-dimethyl-3-hydroxyethyl-9'-methoxyspiro[benz[e]-indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 3,3-dimethyl-1-hydroxyethyl-9'-methoxyspiro[benz[g]-indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 3-carboxyethyl-1,1-dimethyl-9'-methoxyspiro[benz[e]-indolin-2,3'-[3H]-pyrido[2,1-b][1,4]benzoxazine];1-Carboxyethyl-3,3-dimethyl-9'-methoxyspiro[benz[g]-indolin-2,3'-[3H]-pyrido[2,1-b][1,4]benzoxazine]; 1,1-dimethyl-3-hydroxyethyl-9'-methoxyspiro[benz[e]-indolin-2,3'-[3H]-pyrido[2,1-b][1,4]benzoxazine]; 3,3-dimethyl-1-hydroxyethyl-9'-methoxyspiro[benz[g]-indolin-2,3'-[3H]-pyrido[2,1-b][1,4]benzoxazine]; A method comprising: 5-amino-5'-(2-benzthiazolyl)-1,3,3-trimethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 5-amino-5'-(5'-(2-hydroxyphenyl)-2-oxadiazolyl)-1-isopropyl-3,3-dimethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; 5-amino-5'-(5'-phenyl-2-oxadiazolyl)-1,3,3-trimethylspiro[indolin-2,3'-[3H]-naphtho[2,1-b][1,4]oxazine]; or a mixture thereof.; Claim 16 In claim 12, the reactive photochromic compound is 3,3-bis(4-methoxyphenyl)-6,11-dimethyl-13-hydroxyethoxy-13-phenyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-bis(4-methoxyphenyl)-6,11-dimethyl-13-(2-hydroxycarbonylethyl)carboxyethoxy-13-phenyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; 3,3-bis(4-methoxyphenyl)-6,11-dimethyl-13-hydroxy-13-phenyl-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; or a mixture thereof. Claim 17 A method according to any one of claims 1 to 7, wherein the at least one first and second polymerizable material independently comprises at least one polymerizable UV / HEVL absorbing compound. Claim 18 delete

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